Universal method of selective extraction of salts of transition, rare-earth and actinoid elements from combination solutions by means of nanoporous materials

FIELD: metallurgy.

SUBSTANCE: method involves selective extraction of salts in volumes of nanopores of nanoporous conducting materials due to effect of electrostatic interaction of dipole moments of solvated ionic complexes of transition, rare-earth and actinoid elements with electric field of double electric layer of "nanopore wall - solution" boundary line. The method is implemented by subsequent filling of nanopore of nanoporous conducting material with the solution containing ionic complexes of transition, and/or rare-earth and/or actinoid elements, displacement from nanopore of ionic complexes of transition, rare-earth and actinoid elements weakly localised in nanopores by means of pressure of gases or liquids, by filling of nanopore with solution of inorganic acid of high concentration, and by extracting from nanopores of residual ionic complexes of transition, rare-earth and actinoid elements by means of pressure of gases or liquids. The above method can be implemented in an electrochemical cell.

EFFECT: obtaining cheap and competitive compounds of the above elements of high technical purity.

45 cl, 18 dwg, 4 ex

 

The technical field

The invention relates to the production of transition, rare earth and actinoid metals and their compounds, in particular to technology for the selective extraction of salts from multicomponent solutions to produce compounds or concentrates of high purity specified elements.

Prior art

There are various chemical, physical, electrochemical and other methods of extraction of transition, rare earth and actinoid elements from their compounds and solutions, which are widely used in practice to obtain salts of transition, rare earth and actinoid elements. At the heart of these elements is the use of their chemical, physical, electrochemical, and other properties. A common method is the selective extraction from solutions of salts derived from ores with a low content of transition, rare earth and actinoid elements, as well as from industrial and ash wastes. Process for the selective extraction from solutions allows to obtain transition, rare earth and actinoid metals and their salts of high purity.

Usually for selective extraction from solutions of the compounds of each element using separate ways, the principles of selective extraction which is based on the unique properties of ionic complexes of a particular item. This, consequently, leads to a significant complication of extraction technology, to increase the number and list of used chemicals and auxiliary materials, which increases the value of recovered materials. Currently there is no universal method of extraction of salts of transition, rare earth and actinoid elements of multicomponent solutions. It is obvious that the presence of a universal method for extracting elements from a solution will lead, first, to the wide application of this method and, secondly, to dramatically reduce the cost and increase the competitiveness of the obtained materials.

Currently, various methods of selective extraction of transition, rare earth and actinoid elements, which in essence are the closest analogues of the present invention.

In the patent US 6,471,743 the authors describe the methods of removing titanium Ti and other transition metals (Co, Ni, Cu, Mo, Zn, Au and Ag) from ore by dissolving the ore with the use of acids, in particular sulfuric acid with concentration up to 500 g/L. the Time of dissolution in sulfuric acid is from 50 to 120 hours. For selective extraction of elements with sulfuric acid addition is used halide alkali metals and carbon materials as an additive. Also use the decomposition p is water and the selection of the temperature of the process. The addition of carbon materials is used to enhance the reaction kinetics. As the carbon material use graphite or activated charcoal.

In the patent RU No. 2255128 a method for extraction of palladium from waste by dissolving in an aqueous solution containing from 100 to 140 g/l of potassium iodide, 60-80 g/l of iodine, 20-40 g/l of triethanolamine and 5-20 g/l of potassium hydroxide. The extraction process is carried out at the pH and temperature of solution pH=7 to 11 and 20 to 40°C, respectively. This method allows you to get palladium from waste electronic, chemical, electrochemical and jewelry industry.

The method proposed in patent RU No. 2194801 includes electrochemical dissolution of gold and/or silver in an aqueous solution at a temperature of 10-70°C in the presence of complexing agents. As complexing agents used ethylenediaminetetraacetate sodium, the concentration of which is 5-150 g/l Dissolution is carried out at pH of solution pH=7 to 14 and a current density of 0.2 to 10 A/DM2.

The inventors RU # 2097438 patented a method of extracting metals from waste including waste leaching codename solutions containing iodine, washing leached product, electrochemical recovery of gold from production solution, regenerated leach solution and used in leaching. Before Vyselki the of produce chemical enrichment of the sequential extraction of heavy, non-ferrous metals and silver, and the leaching of lead into two stages. The first stage is slightly codename solutions with high concentrations of iodine to extract the main mass of gold, and the second stage with low iodine content to extract gold. From the resulting solutions by electrochemical method to extract gold and simultaneously generate the required amount of iodine. Washing the product from iodide and bound iodine are alkaline solutions with simultaneous conversion of insoluble iodides metal hydroxide, followed by water washing and electrodialysis treatment of industrial water. This leaching lead the agitation method and at wash leached product as an alkaline solution using regenerated production solution.

The method of extraction and separation of non-ferrous and rare metals from aqueous solutions consisting of two stages, is proposed in patent RU No. 2103388. In the first stage, the initial solution is treated with inorganic precipitating with obtaining precipitate carbonates or hydroxides or hydroxocobalamin those elements where the precipitation pH values lower. The resulting filtrate containing elements with a higher pH value of precipitation, is removed from the process as the finished product. The precipitate in the second stage is used as the e precipitator and process source solution. Selected in the second stage precipitate, containing pure elements with a lower pH value, is removed from the process, and the filtrate is treated with inorganic precipitator as in the first stage. In the first stage the pH of the deposition support equal to 2-5 in the second step of 0.5-3.

The method of extraction of rare earth and radioactive metals from oxidized technologically resistant materials proposed by the authors of the patent RU No. 2170775. According to this invention, to obtain rare and radioactive metals from the ash wastes and sulfuric acid are produced sludge is then subjected to processing in the cathode area of the cell under conditions that support the selection at the cathode hydrogen. In the process prepare a slurry with a ratio of solid and liquid phases 5-10 and use the sulfuric acid concentration 50-30 g/L. Electroisolative conducted within a 0.25-1.5 hours, at a cathode current density of 0.5-5 mA/cm2and temperature 18-80°C. Saleslady waste pre-treated with an alkaline solution under conditions of a concentration of 150-250 g/l and temperature of 80-90°C. the processing Time is in the range of 2.0 to 3.0 hours, and the ratio of solid and liquid phases is 1/5. As the cathode using titanium, copper, platinum, Nickel, cobalt, chromium or their alloys.

A known method of extraction of europium, Samar who I am and gadolinium from chloride solutions in the form of salts, shown by the authors of the patent SU 1774670 A1. The invention consists in that in the initial mixture REE serves sulfuric acid. The resulting solution is treated in two filter Presnya pots. In the first cell the solution is pumped through a porous graphite cathode at an apparent current density of 0.95-1.0 A/cm2. Separate the precipitate formed europium sulfate. The mother liquor is treated in the second cell with the apparent current density of 5-6 .5 A/cm2separate the precipitate of sulphate of Samaria and receive a solution containing gadolinium.

In the patent US 7,282,187 the authors describe the process of selective extraction of metals (U, Th, Zr and Sc) from the source of raw materials containing these metals, by shifting them in a soluble state. The extraction process includes the following operations: processing of raw materials first mineral acid to dissolve part of the metal; separating insoluble residues; sludge treatment the second mineral acid to dissolve the remaining metals and extraction of dissolved metal from the aqueous solution.

The authors of the patent US 5,384,104 reveal the methods of extraction of uranium from sediments by direct dissolution precipitation in nitric acid, and treatment solution of carbonate (bicarbonate) sodium. The process of extracting uranium consists of the following operations: oxidation wrans the holding of precipitation, grinding, sorting by particle size, dissolution of particles in the acid neutralization solution carbonate (bicarbonate), obtaining briquettes filtration, washing of the briquettes with obtaining uranium-containing filtrate and the separation of the uranium from the filtrate.

According to the patent RU 2094512 C1, for the selective extraction of uranium from the ore, the ore is subjected to crushing, wet grinding with obtaining pulp and carried out at pH=4.2 to 2.2 in the one or more devices leaching. Next, without performing neutralization at pH=4,6-2.0 leaching process combined with countercurrent sorption of uranium, maintaining the pH in the head in the course of the slurry apparatus ionite processing pH of 4.6-2.6 and pH in the tail apparatus ionite processing 3,4-2,0. The temperature of the acid and ionite processing pulp support 30-70°C. as the oxidant used manganese compounds, desorption of uranium from a busy ion exchanger exercise sulfuric-nitric acid solutions.

In the patent US 4,341,602 the authors explore the ways electrochemical extraction of uranium using oxidation and reduction electrochemical separation cell. The invention relates to the extraction process and increase the concentration of uranium(V1)contained in the organic phase. The organic phase is continuously processed in the contact zone with an aqueous solution containing Oka is lause-reducing agent in a reduced state, and this agent is able to restore U+6to U+4in aqueous solution. The aqueous solution used in the process, comes out partially or completely from the cathode side of the electrochemical separation of cells, under the potential of the constant current, and the aqueous phase leaving the contact zone, partially or fully enters the anode part of the electrochemical separation of the cell.

The above known methods of selective extraction of transition, rare earth and actinoid elements and their salts from multicomponent solutions have disadvantages, which are the main reasons that limit their widespread use. First, it is clear that there is no universal method of extraction of salts of transition, rare earth and actinoid elements of multicomponent solutions. To obtain the offer of the use of multi-stage and complex patterns of selective extraction of elements or their compounds. This significantly increases the cost of the product and reduces its competitiveness. Secondly, mainly using chemical and electrochemical methods of selective extraction, which leads to high costs of technological and auxiliary chemicals, and electricity. Chemical and electrochemical methods are selective and the attraction is often carried out in the presence of solutions to the high toxicity, that requires additional costs for security personnel, waste disposal and has a negative impact on the environment. All the above methods do not solve the problem of getting ultra-high purity of the extracted elements and their individual connections.

Closest to the claimed invention to the technical essence is a method of separating trivalent thallium (III) and trivalent gold (III) with activated carbon, proposed by the authors of scientific publications [1]. To separate these elements were prepared separate solutions of thallium (III) and gold (III). A solution of thallium (III) was prepared by dissolving nitrate thallium Tl(NO)3in 0.05 M sulfuric acid. To obtain a solution of gold (III) metal gold was dissolved in Aqua Regia. Next, the dry residue obtained by thermal evaporation of a specified solution of gold (III)was dissolved in 1 M hydrochloric acid.

The activated carbon in the amount of 100 mg was thoroughly impregnated with 20 ml of a solution of 1 M hydrochloric acid containing 0.02 to 0.2 mg T1(III) and 0.02-2 mg Au(III). Soaked in a mixed solution of the activated carbon was filtered with a paper filter to remove excess solution. Next, the carbon mass were carefully rinsed with solutions of 0.1 M hydrochloric acid and 1 M nitric acid, and obtained the solution was used for elemental analysis by spectroscopy. After washing the carbon material, it was subjected to heat treatment at a temperature of 600°C for 1 hour. The resulting ash was dissolved in Aqua Regia for elemental analysis by spectroscopy.

The results of elemental analysis showed that gold Au(III) from hydrochloric acid solution for two hours almost completely absorbed in the pores of activated carbon. While activated carbon for one hour absorbs a very small amount of thallium T1(III), due to the low rate of absorption T1(III). The repetition of the processes of separation of gold and thallium with different concentrations of Au(III) T1 and(III) in the mixed solution showed that the gold content in the ash is about 97%, and thallium in 1 M nitric acid, obtained after washing the activated carbon, more than 98%.

As can be seen from the above method, after the heat treatment of the activated carbon, the carbon atoms are oxidized to carbon dioxide, and gold Au(III) remains in soot. The ash content of activated carbon is typically 1-5%, depending on the type of the used source material and technologies for the synthesis and activation. Obviously, the gold content of Au(III) in the ash of about 0.4-20%, depending on the concentration of gold Au(III) in solution and ash content in the activated carbon. Ash various activated the s carbon materials is mainly of oxides and carbides of transition and other elements. Therefore, to extract gold from the ashes of activated carbon containing 0.4 to 20% of Au(III), require a different and rather time-consuming process for the selective extraction of gold Au(III) from ash. Therefore, despite the high efficiency of extraction of Au(III) and Tl(III) from a mixed solution with activated carbon, the use of this method for the extraction of gold and thallium in large quantities is not feasible. In addition, this method does not allow to obtain Au(III) high purity.

Brief description of the invention

In the present invention discloses a universal method for the selective extraction of salts of transition, rare earth and actinoid elements of multicomponent acidic solutions containing ionic complexes of transition and/or rare earth and/or actinoid elements. The selectivity of the extraction process mentioned salts from solutions provides electrostatic effect of the interaction of the dipole moments of solvated ionic complexes of the above elements with the electric field created by the electrical double layer (EDL) of the boundary wall of the nanopores - solution" in the volume of nanopores nanoporous conductive materials. According to the proposed invention, the selective extraction of salts is carried out on uma ways.

The first method includes the following processes: filling the nanopores of nanoporous material with a solution containing ionic complexes of the above elements; displacement of nanopores weakly localized in nanopores ion complexes of these elements by the pressure of gases or liquids; filling the nanopores of nanoporous material inorganic acid of high concentration; removing from the nanopores of the residual ion complexes of these elements by the pressure of gases or liquids.

The second method is carried out using a two-electrode electrochemical cell, which consists of the polarizable electrode with a double electric layer, based on nanoporous conductive material, the counter-electrode, a porous separator separating the electrodes of the cell and the housing. The second method includes the processes of: filling the housing of the electrochemical cell with a solution containing ionic complexes of the above elements; filling the nanopores of the electrode based on nanoporous conductive material electrochemical cell mentioned solution; eviction from the housing of the electrochemical cell solution pressure of gases or liquids; filling the housing of the electrochemical cell inorganic acid of high concentration; removing from the nanopores of the residual ion complexes mentioned element is in by the polarization potential of the electrical double layer of the polarizable nanoporous electrode electrochemical cell.

According to this invention, for selective removal of salts of transition, rare earth and actinoid elements of multicomponent solutions are electrically conductive nanoporous materials. The size and specific volume of the nanopores mentioned nanoporous materials are in the range of 0.2 to 5 nm and 0.5-1.5 cm3/g, respectively. Specific surface area of nanoporous materials is in the range of 600-1800 m2/g, and electrical resistivity of 0.01-1000 Ohm·cm For achieving the desired results for the selective extraction of salts of transition, rare earth and actinoid elements of various multicomponent solutions as nanoporous material is nanoporous carbon conductive material, or nanoporous material of the electroconductive titanium oxide, or nanoporous material titanium carbide, or a mixture of different with different combinations.

The essence of a universal method for the selective extraction is that, when filling the nanopores of nanoporous material with a solution containing solvated positive ion complexes of transition and/or rare earth and actinoid elements, which have a dipole moment µ, these ionic complexes are localized in nanopores. This is due to static the WMD interaction of the dipole moment µ ion complexes with the electric field E, created a negative electric charge EDL nanopores in the volume of the mud-filled nanopores. According to this invention, the electrochemical potential of the electrical double layer of nanoporous material containing nanopores multicomponent acidic solutions containing ionic complexes of transition and/or rare earth and/or actinoid elements, is positive relative to the potential of the standard hydrogen electrode (SHE).

In the basis of the proposed universal method for the selective extraction are chemical, electrochemical, physical, and other properties of ionic complexes of transition, rare earth, actinoid elements and nanoporous materials. Careful selection of these parameters nanoporous materials and solutions allows you to create conditions for strong localization in nanopores nanoporous material of the selected type of ion complex of many ion complexes of the above elements is located in a multicomponent solution. Increasing the number of processes of displacement of a mixed solution of nanopores nanoporous material provides a high selectivity of the extraction process and allows to obtain a salt of high purity mentioned elements.

Offer a unique way to extract salt n is readnig, rare earth and actinoid elements of multicomponent solutions using nanoporous materials allows cascading extraction process. In each cascade can be used nanoporous materials with the same or with different parameters. Cascading extraction process allows to obtain a salt of the above elements of ultrahigh purity.

The dielectric constant and the screening length Debye solvent multicomponent acidic solutions containing ionic complexes of transition, rare earth and actinoid elements, ranges from 25 to 100 and from 0.2 nm to 200 nm, respectively. The process of filling the nanopores nanoporous powdered material solution is carried out by mechanical mixing of nanoporous material with the solution, and the resulting mixture is maintained under normal conditions for a period of 1 hour to 20 hours. For maximum filling of the nanopores nanoporous material with a solution of the above mixture is subjected to vacuum. The process of filling the nanopores of nanoporous electrode material with the EDL electrochemical cell with a solution containing the ionic complexes of transition and/or rare earth and actinoid elements, is carried out by filling the cells with a solution and curing under normal conditions for a period of 5 hours to 20 hours. For mA the maximum filling of the nanopores of the above-mentioned electrode with the EDL solution of the electrochemical cell is exposed to vacuum. Desired outcomes selective extraction two methods are achieved when the ratio of solution volume to the total volume of the nanopores nanoporous powdered material and the electrode material with the EDL electrochemical cell, respectively, from 0.5 to 1.2 and from 0.8 to 1.2.

The displacement of the nanopores nanoporous carbon material ion complexes is carried out by the pressure of gases (e.g. air, nitrogen, carbon dioxide or various mixtures), which leads to the destruction of the nanopores poorly localized ion complexes of the above elements. In nanopores remain, basically, only ion complexes of those elements, which are strongly localized in nanopores, and poorly localized ion complexes are concentrated in the extruded from the nanopores solution. Then there is selective separation of ionic complexes of the initial solution. When this ion complexes of some types of items remain in nanopores, and other types of items become overset solution.

The process of extracting residual nanopores ion complexes is carried out using an aqueous solution of inorganic acids of high concentration (for example, aqueous solutions of hydrochloric acid, sulfuric acid, phosphoric acid, hydrofluoric acid and their mixtures) or polarization potential of nanoporous material. Polarization is otential nanoporous material in the opposite area from the equilibrium potential changes the direction of the electric field strength E. Therefore, the interaction of the dipole moment µ ion complexes of elements with the field E pushes them out of the nanopores. This option extract ion complexes of elements of nanopores nanoporous material has high controllability, performance, and cost-effective and convenient for industrial applications.

This invention relates to selective extraction of salts of transition, rare earth and actinoid elements from solutions using conductive nanoporous materials. The generic method is designed to extract transition, rare earth and actinoid elements of the respective ores with low content of extractable elements, as well as from various industrial and ash wastes. The proposed generic method allows to obtain transition, rare earth and actinoid metals and their salts high and ultra-high purity. This nanoporous material is used multiple times.

Thanks to the original technological, technical and design solutions, as well as the universality of the method for the selective extraction of salts of transition, rare earth and actinoid elements of multicomponent solutions using nanoporous materials, the proposed method, in contrast to known methods of selective extraction, allows the floor is icy salt of the above elements in industrial quantities required high purity and low cost. We also offer a universal method allows to enrich multicomponent solutions containing ionic complexes of transition, rare earth and actinoid elements of the selected component ion complex.

The essence of the proposed universal method for the selective extraction of various salts of transition, rare earth and actinoid elements of multicomponent acidic solutions using nanoporous conductive materials is illustrated in the following detailed description of physical processes filling the nanopores of nanoporous material solution and the selective extraction of nanopores salts of the specified elements. The disclosure of the essence of the present invention is also illustrated by a detailed description of the interaction of the dipole moments of solvated ionic complexes of transition, rare earth and actinoid elements with the electric field of the electrical double layer boundary wall of the nanopores - solution", specific examples of selective extraction of salts of transition and rare earth elements, detailed analysis of the results and the following figures.

Brief description of figures

Figure 1. The module of the electric field strength |E| dual electric field along the diameter of the mud-filled nanopores nanoporous what about the material. Designation: dcmthe wall thickness of the nanopores; Dporesthe diameter of the nanopores and LD is the length of the Debye shielding in the volume of the nanopores.

Figure 2. The scheme of extraction become six-coordinated ionic complex of trivalent metal ion Me3+of nanopores nanoporous material using an aqueous solution of hydrochloric acid of high concentration.

Figure 3. The scheme of extraction become six-coordinated ionic complex of trivalent metal ion Me3+of nanopores nanoporous carbon material by the method of polarization potential of the electrical double layer.

Figure 4. The design of the device for selective extraction of transition and rare earth elements using nanoporous carbon powder.

Figure 5. Absorption spectra of 1% mixed source of an aqueous solution of chloride NiCl2+CrCl3(1)after the first (2), sixth (3), eighth (4) and ten (5) processes of displacement solution of the nanopores NPC powder, in the spectral range 200-1000 nm.

6. Absorption spectra of the test aqueous solutions of chloride NiCl2(1), CrCl3(2) and a mixed aqueous solution of NiCl2+CrCl3(3) in the spectral range 200-1000 nm.

7. Absorption spectra of 1% mixed source of an aqueous solution of chloride CoCl2+NiCl2+CrCl3(1)after the first (2) and fifth (3) processes of displacement solution of the NAS is then NPC powder, in the spectral range 200-1000 nm.

Fig. Absorption spectra of the test aqueous solutions of chloride CoCl2(1), NiCl2(2), CrCl3(3) and 1% mixed aqueous solution of CoCl2+NiCl2+CrCl3(4) in the spectral range 200-1000 nm.

Fig.9. Absorption spectra of 1.5% mixed source of an aqueous solution of chloride NiCl2+TiCl3(1)after the first (2)second (3)third (4) fourth (5) processes of displacement solutions of the nanopores NPC powder, in the spectral range 200-1100 nm.

Figure 10. Absorption spectra of the test of 1.5% aqueous solutions of the chloride NiCl2(1), TiCl3(2) and a mixed aqueous solution of NiCl2+TiCl3(3)in the spectral range 200-1100 nm.

11. Absorption spectra of distilled water (1), 37% aqueous hydrochloric acid solution (2) and an empty cell K10 (3), in the spectral range 200-1100 nm. Measuring the transmittance of the solution was carried on air.

Fig. The structure of the octahedral complex of hydrated ferric ion titaniumand the splitting pattern of Terma2D free ion Ti3+(d1in octahedral ligand field H2O taking into account the Jahn-teller effect (b).

Fig. Absorption spectra of hexagonal complexesandin aqueous solutions 1% (1), 5% (2) and 37% hydrochloric acid, in petrolina the range 200-1100 nm.

Fig. The design of the two-electrode electrochemical cell with nanoporous carbon plates.

Fig. The kinetics of the voltage U, the potential of the EDL nanoporous carbon plate & Phi;CPand the counter-electrode of the Grafoil φGR(relative to the potential of the reference electrode, SHE) EU-cells during long-term storage of cells with 1.5% aqueous solution of trichloride titanium.

Fig. Absorption spectra of 1.5% of the initial aqueous solution of trichloride titanium TiCl3(1), solution EU-cells after 55 time storage (2), after the polarization of the coal plate (3), in the spectral range 200-1100 nm.

Fig. Absorption spectra of aqueous solutions of sulfates Eu2(SO4)3(1), Nd2(SO4)3(2) and Eu2(SO4)3+Nd2(SO4)3(3) in the spectral range 380-600 nm.

Fig. Absorption spectra of the source of an aqueous solution of sulphate Eu2(SO4)3+Nd2(SO4)3(1) and extruded from the nanopores of nanoporous powder solution (2), in the spectral range 380-610 nm.

Detailed description of the invention

Currently, there are various chemical, physical, electrochemical and other methods of extraction of transition, rare earth and actinoid elements of their various compounds and solutions. These methods are widely used in practice to obtain RA is personal salts and pure materials transition, rare earth and actinoid elements. At the heart of transition, rare earth and actinoid elements is the use of their chemical, physical, electrochemical, and other properties. To extract transition, rare earth and actinoid elements of the respective ores with low content of extractable elements, as well as from various industrial and ash waste, use, basically, the method of selective extraction from solutions. This method allows to obtain transition, rare earth and actinoid metals and their salts of high purity. In accordance with well-known methods are chemical, electrochemical, physical, and other properties of ionic complexes of transition, rare earth and actinoid elements.

Chemical, electrochemical, physical, and other properties that are commonly used in practice for the selective extraction of many ion complexes of transition elements in different solutions are quite similar. For example, the above-mentioned properties of ionic complexes of all rare earth elements are virtually identical. Also similar properties shows the main part of the actinoid elements. These features due to the current lack of a universal method for extracting compounds of transition, rare earth and actinoid is a separate estimate of multicomponent solutions. Usually for selective extraction from solutions of the compounds of each element in practice, the use of individual methods, the principles of selective extraction which is based on the unique properties of ionic complexes of individual elements. This often leads to a significant complication of extraction technology, to increase the number and list of used chemicals and auxiliary materials, which increases the value of recovered materials.

The present invention provides two universal method for the selective extraction of salts of transition, rare earth and actinoid elements of multicomponent acidic solutions containing ionic complexes of the above elements. In contrast to known methods of selective extraction, the proposed methods allow high selectivity to extract from multicomponent solutions of different compounds with very similar chemical, electrochemical, physical and other properties of transition, rare earth and actinoid elements.

Transition metals are widely used in almost all fields of technology, energy, transport, space, communication, etc. the Most common and used transition metals are mainly from their different chemical compounds by the way, by PR the interstitial treatment and recovery of an appropriate reducing agent. Also practice using the methods of obtaining transition metal electrochemical recovery from solutions of their soluble salts and electrolysis of melts corresponding compounds of metals.

With the rapid development of technology microelectronic devices, chemical power sources, nuclear energy, and other technologies needed transition metals and their compounds of high purity. To ensure the needs of industry developed such important methods of purification: distillation in a vacuum; zone melting; thermal decomposition of volatile compounds of transition metals; ideny way. All these methods are rather time-consuming ways. Despite the possibility of obtaining a number of transition metals (Ti, Ni, Zr and others) is sufficiently high purity production by iodide method, the obtained metals have a high price, and this method has high toxicity caused by the use of iodine.

Rare earth elements (REE) are widely used in various fields of engineering, technology and science. The main part of the REE and their oxides used in metallurgy, mechanical engineering, nuclear engineering, chemical industry, electronic industry and instrument making. Mechanical, thermal and electrochemical properties of many alloys significantly improved with the application of the AI additives from REE. With the use of oxides of rare earth elements are made of special glass, which have high transparency optical radiation in the visible and infrared optical radiation. Various compounds of the REE in the chemical industry used in the manufacture of varnishes, pigments and paints. Cushioning REE hydrogen and nitrogen can be used as getpagetitle. Thanks to special quantum properties of 4f-4f transitions of rare earth elements, they are widely used in many quantum generators, production of active nonlinear elements of optoelectronics and various phosphors.

Since the basic properties of rare-earth elements with atomic numbers Z=58-71, in addition to cerium, are similar enough, the technology of separation of these elements is quite complex and time consuming process. Usually, the main part of the compounds of rare-earth elements extracted from various solutions by precipitation as oxalate or double sulfates of rare earth elements and sodium. Further, salts of rare earth elements, with the necessary degree of technical purity, obtained from these compounds. For the separation of cerium from other rare earth elements, in which the compounds are trivalent, uses the ability arunachalis in the tetravalent state. Therefore, usually the cerium from other rare earth elements is separated by its oxidation to the tetravalent state. Europium and other rare-earth elements are separated using the low solubility of divalent europium sulfate. Trivalent europium sulfate, which has high solubility, reduced to ferrous sulfate.

Usually, to obtain a rare earth metal elements in the industry popular method of recovery of the halides of the corresponding elements by electrolysis of melts or calcium. To obtain metal REE high purity is required ways to obtain their halides of high purity.

Important chemical elements for use in power generation, weapons, science, engineering, and medicine are the actinides with atomic numbers Z=90-103. Of these actinides in nature common are practically the only elements of U and Th, as well as in small quantities occurs in RA. Other actinides are found in nature and their synthesized artificially. The elements U and Th are the original source for the synthesis of other important elements, for example, Pu and Np, for their practical application. The actinides U, Th, Pu and Np are used in nuclear power, nuclear weapons, nuclear power sources for space vehicles and systems, and different is blastah of science and technology.

It is known that the actinoid elements with atomic numbers Z=90-103 in many compounds show different valence. Thus the values of Gibbs energy of ion complexes of actinides in different oxidation States have very similar values. Therefore, the solutions can be ion complexes actinoid with different charge States. For example, in acidic solutions are ionic complexes of Pu with charge state from +3 to +6. For compounds of actinides in aqueous solutions characterized by hydrolysis, polymerization, complexation, formation of insoluble fluorides, and other reactions caused by intensive samoobucheniu. The practice is widely used, mainly, the above features of the actinides for their separation. Because the actinoids are easily transferred from one oxidation state to the other, for their separation also use redox reaction. For example, ion Th4+is a good complexing agents and ion U6+forms insoluble fluoride (UO2F2), which allows to obtain chemical compounds of these elements, using the characteristics of complexation and formation of insoluble fluorides.

In the present invention discloses a universal method for the selective extraction of salts PE achtnich, rare earth and actinoid elements of multicomponent acidic solutions containing ionic complexes of transition and/or rare earth and/or actinoid elements. The selectivity of the extraction of the mentioned salts is carried out by the electrostatic effect of the interaction of the dipole moments of solvated ionic complexes of transition, rare earth and actinoid elements with the electric field created by the electric double layer boundary wall of the nanopores - solution" in the volume of nanopores nanoporous conductive materials. According to the proposed invention, the selective extraction of salts is carried out in two ways.

The first method includes the four following process:

1. filling the nanopores of nanoporous material with a solution containing ionic complexes of the above elements;

2. the displacement of the nanopores weakly localized in nanopores ion complexes of these elements by the pressure of gases or liquids;

3. filling the nanopores of nanoporous material inorganic acid of high concentration;

4. extract from the nanopores of the residual ion complexes of these elements by the pressure of gases or liquids.

The second method is carried out using a two-electrode electrochemical cell, which consists of the polarizable electrode with double the output electric layer, based on nanoporous conductive material, the counter-electrode, a porous separator separating the electrodes of the cell and the housing. The second method involves five sequential process:

1. fill the housing of the electrochemical cell with a solution containing ionic complexes of the above elements;

2. filling the nanopores of the electrode based on nanoporous conductive material electrochemical cell mentioned solution;

3. eviction from the housing of the electrochemical cell solution pressure of gases or liquids;

4. fill the housing of the electrochemical cell inorganic acid of high concentration;

5. extract from the nanopores of the residual ion complexes of these elements by the polarization potential of the electrical double layer of the polarizable nanoporous electrode electrochemical cell.

The proposed generic method allows selective extraction from multicomponent acidic solutions containing ionic complexes of transition and/or rare earth and/or actinoid elements, salts of these elements of high purity. The selectivity of separation of ionic complexes provides a conductive nanoporous material. For the first method of selective separation is used nanoporous material in the form of powder is s, or granules, or fibers, or plates, or disks. Since the rate of filling of the nanopores nanoporous material with a solution essentially depends on the size, shape and wettability of nanoporous materials, preferred is the use of nanoporous materials in the form of powders and granules. Application of nanoporous materials in the form of powders and granules allows the separation process in large volumes and in a short time.

Nanoporous materials-electrode electrochemical cell, for the second method of selective separation, used in the form of plates, or briquettes, or disks. The mentioned materials are made of nanoporous carbon powder and a polymeric binder materials. For the polarization potential of nanoporous electrode electrochemical cell with low energy loss, you must use nanoporous materials with low resistivity. Preferred is the use of nanoporous materials with electrical resistivity in the region of 0.05-100 Ohms·cm, depending on the geometric dimensions of the mentioned materials.

From numerous studies it is well known that when filling the nanopores of nanoporous material with a solution (electrolyte) on the boundary wall of the nanopores - solution" occurs dual electric the definition layer. In the walls of the nanopores and the solution having space charge region (SCR). The magnitude and sign of the electrochemical potential of the EDL depend on fundamental parameters of nanoporous material and solution. At high concentrations of free charge carriers in the walls of the nanopores nanoporous material, electric charge, respectively, and the electrochemical potential of the EDL side walls of the nanopores localized in thin surface layers of the nanopores. The thickness of the SCR carbides and oxides of transition metals with high conductivity is in the range of 0.1-0.5 nm, depending on the type of material, and in a wide range of potentials practically does not depend on the potential value of the EDL. Typically, the concentration of free charge carriers in the walls of the nanopores of nanoporous carbon materials in more than 500 times smaller than the corresponding parameter of carbides and oxides of transition metals. Therefore, first, the thickness of the SCR in the walls of the nanopores conductive nanoporous carbon materials is significantly greater than the thickness SCR oxides and carbides of transition metals. Secondly, the thickness of the SCR nanoporous carbon materials depends on the capacity of the EDL.

Usually the equilibrium electrochemical potential of the EDL various carbon materials with a crystal lattice of graphite in various electrolytes have similar values and are in the range of 0.5-0.6 In (relative to the potential SHE). Specific electric capacitance of the EDL nanoporous carbon materials in the range of potentials of 0.2-0.6 (relative to SHE), which is used in the present invention, is 120-800 f/g, depending on the size of the nanopores, the distribution of nanopores in size, the concentration and type of solution. Specific electric capacitance of the EDL nanoporous carbide and oxides of transition metals in the specified range potentials practically does not exceed 100 f/, the capacitance of the EDL nanoporous materials, in addition to the parameters of the porous structure also significantly related to the types and densities of surface States. Since the cost of nanoporous carbon materials smaller than the corresponding parameters of nanoporous carbide and oxides of transition metals, and nanoporous carbon materials have a higher chemical stability in concentrated solutions of inorganic acids, preferred is the use of nanoporous carbon materials.

In the present invention are used nanoporous materials, the equilibrium electric double layer which consists of negative ions are localized on the surface States from the solution (electrolyte), and holes in the space charge region of the walls of the nanopores. Negative when the second charge, localized surface States of the walls of the nanopores in the volume of the nanopores creates an electric field E, the value of which decreases with distance from the wall to the center of the nanopore (Figure 1). The distribution of the electric field E in nanopores is characterized by the length of the Debye shielding, which is determined by the formula

where: ε is the dielectric constant in the nanopores of a solution (aqueous solution of ε≈80); ε0is the permittivity of vacuum (ε0=cent to 8.85·10-14F/cm); k - Boltzmann's constant (8,629·10-5eV/K); Z and N are respectively the charge and concentration (cm-3) anions or cations of the solution. From the formula (1) implies that in highly diluted aqueous solutions of the screening length LD reaches tens of nanometers, and in concentrated solutions - tenth of a nanometer. For example, the value of LD for 1% aqueous solution of hydrochloric acid is 0.58 nm, at a temperature of T=300 K. Therefore, the magnitude of the electric field E created by the charge of the surface States, in the Central part of the nanopores with a diameter of about 1.6 nm will decrease in e times. It is obvious that the dipole moment µ of ionic metal complexes will strongly interact with the field E in the whole volume of nanopores with diameters of not more than 1.6 nm. It locates and holds the charged comp is exy metals in the volume of the nanopores.

As follows from the above formula (1), the degree of localization in nanopores ion complexes of metals depends on such parameters as the size and shape of the nanopore; the acidity and composition of the solution; the potential of the EDL and the electrical capacity of the boundary wall of the nanopores - solution"; geometrical dimensions, symmetry, the dipole moment and the electric charge of the ionic metal complexes. The main parameters (the capacitance of the EDL, the size and shape of the nanopores, specific surface area, density of the main charge carriers of the walls of the nanopores, etc.) nanoporous materials, as shown by the authors [2], are interrelated. The selectivity of the extraction ion complexes of various transition, rare earth and actinoid elements are strictly related with the dimensions of the nanopore, the distribution of nanopores by their size, specific electric capacitance of the EDL, as well as with the properties of the solution and the value of the dipole moments of these complexes. The degree of selectivity of the extraction process is also related to the variance of the distribution of the nanopore size of nanoporous materials. Obviously, by selecting the dimensions of the nanopores, the desired solvent and concentrations of ionic complexes of transition, rare earth and actinoid elements can provide high selectivity of the extraction process their ion complexes, taking into account dipole who's last moments.

According to this invention, when filling the nanopores of nanoporous material multicomponent solution containing the ionic complexes of transition and/or rare earth and/or actinoid elements, ionic complexes are localized in nanopores. Depending on the geometric dimensions and shape of the nanopore, the magnitudes of the dipole moments µ ion complexes, the concentration of anions (cations) and the dielectric constant of a multicomponent solution localization of different ionic complexes occurs by various forces. The displacement of the nanopores nanoporous material multicomponent solution pressure of gases or liquids leads to the destruction of the nanopores weakly localized in nanopores ion complexes. Strongly localized ion complexes remain in nanopores nanoporous material that ensures the selectivity of separation of ionic complexes. Removing residual (highly localized) in nanopores of nanoporous materials and nanoporous electrode electrochemical cell ion complexes is carried out in two different ways. Retrieving by the first method (from nanopores nanoporous material) is made by filling the nanopores of nanoporous material with a solution of inorganic acid and high concentrations of preemptive solution of nanopores pressure of the gas or zhidkometallicheskie on the second way (from the nanopores of nanoporous electrode electrochemical cell) is the polarization potential of the EDL polarizable electrode-based nanoporous material in the opposite direction the equilibrium potential values.

The overwhelming proportion of ionic complexes of salts, soluble in water and acidic environments, transition, rare earth and actinoid elements is, basically, become six-coordinated, and five-coordinated, cosmicvariance and chetyrehsharnirnymi complexes. The dipole moments µ become six-coordinated (hexagonal) and chetyrehdorozhechnyh (square planar) ion complexes of transition, rare earth and actinoid elements in different solutions usually have small value, under normal conditions, as, for example, hexagonal ion complex of divalent Nickelat low concentrations in aqueous solution. Small value of the dipole moment of such complexes leads to weak electrostatic interactions with the field E and, respectively, to weak localization in nanopores. This allows you to effectively displace such ion complexes of small nanopores pressure of water (examples 1-4).

Note that if the free ion complex has no dipole moment, under the influence of the field E, and the interaction of these complexes with ions and dipole moment of the solvent molecules, is the axial distortion of the symmetry of the complex, resulting in an induced dipole moment. So who is one occurrence of strong localization of such ion complexes in nanopores of a certain size. Our research has shown that symmetry become six-coordinated ion complexes of Nickelin an aqueous solution of hydrochloric acid is almost not distorted in a wide range of concentration of hydrochloric acid. A small distortion of symmetry is observed only at high concentrations of hydrochloric acid. This circumstance allows us to effectively displace water from the nanopores of the carbon powder with the size of the nanopores in the range of 0.2-5 nm complexes. Unlike ionic complex of Nickelhexagonal ion complex titaniumin aqueous solution has a strong axial distortion. Our extensive research has allowed to establish that the symmetry of hydrated ionic chromium complexmuch depends on the composition of the aqueous solution. Note that even at very low concentrations, complexin solution there is a strong axial distortion of the symmetry of the complexes. The axial distortion of the symmetry of the ion complexes,and also other complexes of transition, rare earth and actinoid elements leads to an induced dipole moment. This si is Ino localizes these ionic complexes in nanopores nanoporous material.

Important technological point universal selective extraction for industrial applications, is the process of extracting from the nanopores residual, highly localized ion complexes of transition or rare-earth or actinoid elements. The process diagram of the first variant of the extracted ion complexes of nanopores shown in figure 2. To demonstrate the extraction process is highly localized ionic complex of nanopores nanoporous material as the ion complex is taken hydrated treasurary ion complex metal. To extract ion complexes of the nanopores used an aqueous solution of hydrochloric acid of high concentration. This method of extraction of the ion complexes is a simple way and can be widely used for production of metal compounds and/or metals in large quantities.

As can be seen from Figure 2, under a single nanopores positive charge of the ion complexcompensated by the negative charge of the chloride ions and, accordingly, remains electroneutrality particles nanoporous material. Hydrated protons and chloride ions from aqueous solution of hydrochloric acid can easily penetrate into the nanopores, which contain ionic complex metaland the water molecule is. This is due to the small size, dipole moments and low numbers of hydration of these ions. For example, we note that the effective radius, hydration number and the dipole moment of chlorine ion Cl(H2O)-is, respectively, of 0.25 nm, 1 and 1.05 D. Since the dielectric constant of hydrochloric acid and water are, respectively, 80 and 6.4, the value of the dielectric constant of an aqueous solution of hydrochloric acid depends on the concentration of the latter. According to the present invention, the optimum concentration of hydrochloric acid is determined taking into account the main parameters of the nanoporous material and specific extractable complex of the transition or rare earth or actinoid element.

Penetration of hydrochloric acid in the volume of the nanopores nanoporous material reduces the parameter ε of the solution in the nanopores. This leads to a significant decrease of the Debye length and, consequently, a sharp weakening of the localization of the ion complex in the nanopores. So hydrated protons and chloride ions in nanopores replace ion complexand part of the water molecules, displacing the last volume of the nanopores, as schematically shown in figure 2. The results of our research showed that the use of nanoporous material with dimensions of the nanopores in the range of 0.2 to 5 nm, the residual suitable liquids, to extract from the nanopores of hydrated complexes of various transition, rare earth and actinoid elements are liquids with a dielectric constant of not more than 20. Despite the fact that the permittivity of hydrochloric and hydrofluoric acids is about 84, small radii and hydration numbers of ions of these acids create a favorable condition for their use. For example, the effective radius and hydration of the ion numberhave a value of 0.26 nm and 1, respectively, this greatly facilitates and accelerates the process of their penetration into the nanopores. The poet use of other inorganic acids, except hydrochloric acid, involves the preparation of the various solutions with a dielectric constant of not more than 20, for the recovery of hydrated ion complexes of the nanopores.

According to the proposed invention, the specific surface area of nanoporous material of the first method for the selective extraction is in the range of 600-1800 m2/, At the same time, to obtain the desired results of the selectivity of the extraction of ionic complexes of transition and/or rare earth and/or actinoid elements of multicomponent solutions, the dimensions of the nanopores nanoporous material should be in the range of 0.2 to 5 nm, and the specific volume of the nanopores in the range of 0.5-1.5 cm 3/, When using nanoporous carbon materials and nanoporous materials from conductive oxides and carbides, the preferred ranges of specific surface area and specific volume of the nanopores are: 1200-1800 m2/g and 0.8-1.5 cm3/g; 600-1200 m2/g and 0.5-1.2 cm3/g, respectively.

The proposed first method of extracting compounds of transition, rare earth and actinoid elements of multicomponent solutions using nanoporous materials allows for both multiple and cascading processes of extraction. To obtain soluble compounds of these elements ultra-high purity, the extracted solution with residual ionic metal complexes of nanopores nanoporous material is subjected to re-extraction process. This procedure is repeated to achieve the necessary technical purity of the compounds. In all the processes of extraction used one and also nanoporous carbon material.

Cascade process for the selective extraction enables you to separately extract all the components of the multicomponent solution. The parameters of nanoporous materials all cascades are selected so that in the nanopores of nanoporous materials each cascade is strongly localized only ion complexes one typemetal. The process of selective extraction is carried out consistently with the United cascades. After the process of displacement solution of the nanopores nanoporous material of the first cascade, the extruded solution is fed to the second stage, and from the second stage to the third stage and so on After the above-mentioned process in nanopores nanoporous material of each of the cascade there is a strong localization only ion complexes of the same type of metal. Forth from the nanopores of nanoporous materials each cascade separately extracted residual nanopores ion complexes of metals.

The scheme of the second method of extraction of the residual ion complexes of transition, rare earth and actinoid complexes of nanopores nanoporous material is shown in Figure 3. The polarization potential φ-nanoporous material in the region of negative values changes the sign of the charge SCR walls of the nanopores and the direction of the field strength that is, When the polarization potential of nanoporous material in the negative region ionized surface States are restored, a new electric double layer of excess electrons in the surface layers of the walls of the nanopores and protons from solution, in the case of multicomponent aqueous solution (Figure 3). The interaction of the dipole moment µ ion complex will solem E, after changing its direction, to cause it to eject ion complexes of metals of the volume of the nanopores. Since the polarization potential of nanoporous material is held in the environment of the electrolyte of an aqueous solution of acid, then forced out of the nanopore ion complexes into solution, which is forcibly separated from the nanoporous material. The surface-state density nanoporous. carbon conductive materials and conductive nanoporous materials of oxides and carbides of transition elements, create a small capacity electric double layer.

The used quantity of electricity q when the polarization potential of the EDL nanoporous material & Phi;0to the required φ values to retrieve from the nanopore ion complexes according to the second proposed method has a direct dependence on the values of specific electric capacity and is expressed by the formula:

where C is the capacitance of the polarizable electrode electrochemical cell. When using nanoporous materials with low specific electric tanks require low power consumption. The selectivity of the extraction of the specific element according to the invention depends on the size of the nanopores and the specific surface area of nanoparticulation. Therefore, the desired result of selective extraction ion complexes of a particular element with a minimum energy consumption is achieved by an optimal choice of the size of the nanopores and the specific surface area of nanoporous material.

Specific electric capacity Cmnanoporous material of the polarizable electrode with the EDL is associated with a specific pasadu surface by the following formula:

In the formula (3) ε is the dielectric constant of the solution in the space charge region of the EDL. The parameters Smand d is the specific surface area and the effective thickness of the EDL, respectively. The electric field in the volume of the SCR reaches a sufficiently large value that leads to a significant reduction of the dielectric permittivities of almost all solutions. For example, the value of ε of water in a dense region of space charge EDL decreases from 80 to 6 [3]. The region of space charge from the electrolyte consists of two consecutive layers. The first dense layer (Helmholtz layer) is formed on the surface of the walls of the nanopores, and the second layer (diffusion layer) is formed after the layer Helmholtz. Usually the value of the layer thickness of the Helmholtz LGweakly depends on the ion concentration of solutions, types of solvents and is in the range of 0.3-0.5 nm. Strata is and diffuse layer L dmuch depends on the ion concentrations of solutions and solvents. In highly dilute solutions, the value of Ldreaches tens of nanometers, and in concentrated solutions - tenth of a nanometer.

Since the electric capacitance Helmholtz layer and the diffuse layer are connected in series, from the above analysis it follows that the dominant contribution to the electrical capacitance of the EDL has a capacity of Helmholtz layer. To this total capacitance of the EDL connected in parallel other capacity, caused by surface States. The electric capacity of the surface States has significant value only in nanoporous carbon materials in the field capacity minus 0.25 - minus 0.55 In (relative to SHE). The nanoporous carbide and oxides of transition metals the electrical capacity of the surface States in a wide range of potentials is small compared to the total capacity of the EDL. As mentioned above, according to the present invention, the potential of nanoporous carbon electrode electrochemical cell is polarized in the range from 0.6 to 0.2 In (relative to SHE). The polarization potential of nanoporous carbon materials in the specified range does not change the density of surface States, and, accordingly, the total capacitance of the EDL nanoporous ug is erodov used in the range of potentials is practically unchanged.

To assess the specific electric capacitance of nanoporous material with a specific surface area of 1400 m2/g assume that the average value ε of the solution in the space charge region of the EDL nanopores is 20, and the magnitude of the effective thickness of the EDL - 0,6 nm. For specific electric capacitance of the formula (3), we obtainm=413 f/g From the formula (2), taking into account the value of Cm(413 f/g), it follows that the maximum value of the specific quantity of electricity for the polarization potential of nanoporous electrode electrochemical cell from 0.6 to 0.2 In is 330,4 CL/g (91,8 mA·h/g).

According to the proposed invention, for the manufacture of nanoporous electrode material for electrochemical cells use materials with specific surface area in the range of 500-1400 m2/, At the same time, to obtain the desired results of the selectivity of the extraction of ionic complexes of transition and/or rare earth and/or actinoid elements of multicomponent solutions, the dimensions of the nanopores nanoporous material should be in the range of 0.2 to 5 nm, and the specific volume of the nanopores in the range of 0.5-1.4 cm3/, When using nanoporous carbon materials and nanoporous materials from conductive oxides and carbides preferred ranges of specific surface area and specific volume n is nopar are: 1200-1400 m 2/g and 0.8 to 1.4

cm3/g; 500-1100 m2/g and 0.5-1.1 cm3/g, respectively.

When the polarization potential of nanoporous electrode electrochemical cell on the counter-electrode oxygen is liberated. Obviously, the counter-electrode must be resistant to atomic oxygen and to have stable settings with multiple polarization potential in concentrated solutions of mineral cicloturismo electricity when the polarization potential of nanoporous electrode electrochemical cell, in addition to the specific electricity nanoporous electrode, also depends on the voltage of the cell. To obtain the minimum value cell voltage as the counter-electrode materials with low overpotential of oxygen evolution. Suitable materials are noble metals, their oxides and conductive oxides of transition metals, with low values of the overvoltage of the oxygen release of these materials. Preferred materials for the counter-electrode are noble metals, noble metal oxides and their various combinations.

The electrical resistance of the two-electrode electrochemical cell depends on the resistivity of the solution and the resistance of the counter-electrode, nanoporous electrode and the porous separator. To reduced the I cost of electricity when the polarization potential of nanoporous electrode electrochemical cell, according to the present invention, the cell used porous separators and the collector current of nanoporous electrode of the constant used in the solutions of materials with high electrical conductivity.

Offer a second way to extract compounds of transition, rare earth and actinoid elements of multicomponent solutions using a two-electrode electrochemical cell with the polarizable electrode-based nanoporous materials allows for both multiple and cascading processes of extraction. To obtain soluble compounds of these elements ultra-high purity, the extracted solution with residual ionic metal complexes of nanopores nanoporous electrode is subjected to re-extraction process in the electrochemical cell. This procedure is repeated to achieve the necessary technical purity of these compounds. All processes of extraction is conducted using a single electrochemical cell.

Cascade process for the selective extraction allows you to retrieve all ion complexes of transition, rare earth and actinoid elements of the multicomponent solution. For cascade extraction is going to cascade from a variety of two-electrode electrochemical cell. The buildings all cells are connected posledovatelnuju other polymer tubes for transferring a multicomponent solution of cells. Current findings protivoelektrodom all cells connected to the positive pole of the current source and the current findings collector current of nanoporous electrodes of all cells to the negative pole. The parameters of nanoporous electrodes of all cascades are selected so that in the nanopores of nanoporous electrode of each cascade is strongly localized only ion complexes of the same type of metal. After the process of displacement solution of the nanopores nanoporous material of the first cascade overset solution is fed to the second stage, and from the second cascade after displacement is fed to the third stage and so on After the process is complete displacement solution of the nanopores nanoporous electrode of the last cascade in nanopores nanoporous material of each cascade is strongly localized only ion complexes of the same type of metal. Next, close the input and output transfer solution all stages, the buildings all cells are filled with concentrated inorganic acid and polarize the potential of nanoporous electrodes of all cells, using a current source. This leads to the extraction solution with a specific type of ion complexes of nanopores nanoporous material of each cascade separately

Despite the consumption of a small amount of electricity, for a polarization potential of nanoporous electrode e is estrogenically cell this method of selective extraction of ionic complexes of transition and/or rare earth and/or actinoid elements of the nanopores nanoporous material is a universal method, has a high controllability and performance, but also economical and convenient for industrial applications.

According to the present invention, the extraction of 1 gram of pure compounds of the above elements in the first and second methods required approximately from 20 to 100 grams of nanoporous carbon material, depending on the type and extent of technical purity compounds. The value of the extracted compounds of the above elements largely depends on the cost parameters and operational resource nanoporous material. The price of 1 kilogram of nanoporous carbon material in the form of a powder, is preferred for the selective extraction of ionic complexes of transition, rare earth and actinoid elements, on the world market at the present time is about $ 12. We offer first and second methods allow repeated use of nanoporous materials. This allows you to get cheap, high purity and competitive compounds different transition, rare earth and actinoid elements.

Although the invention examples of selection the th retrieval using multi-component solutions, representing aqueous solutions and aqueous solutions of hydrochloric acid, it is possible to use other solutions, on the basis of inorganic and organic solvents with a dielectric constant in the range of 25-100. Also when removing from the nanopores in the examples used only aqueous solutions of hydrochloric acid of high concentration. It is possible that the use of different mixtures of aqueous solutions of other inorganic acids will increase the efficiency of extraction of the ion complexes of the nanopores of nanoporous materials. Obviously, the performance, the degree of technical purity and other parameters of the first and second methods of selective extraction depend on the structures of the apparatus, two-electrode electrochemical cell for selective extraction and units for cascading extraction process.

These and other obvious modifications are within the scope of the present invention is characterized by the following claims.

Examples of carrying out the invention

Example 1. To demonstrate the efficacy of selective extraction of transition metal salts of the claimed method was carried out the separation of the chlorides of Ni and About their mixed aqueous solution. The extraction process was carried out using a device (1), the design of which is shown in Figure 4. Case (2), upper (3) and not the latter (4) cover, fittings pressure (5) and outlet (6) of the device (1) made of Teflon to avoid ingress of foreign elements into a solution of parts of the device. As nanoporous material was used nanoporous carbon (NPC) powder (7), which were placed in the working volume (8) of the device (1). To prevent migration of particles of carbon powder in the Kiddle solution was used nanoporous filter (9), based on nanoporous carbon material, and a ceramic filter (10). Nanoporous filter (9) was made on the basis of nanoporous carbon powder and a binder material PTFE. This design provides high chemical resistance in all solutions of inorganic acids of high concentration.

For the research process for the selective extraction of elements was used NPC powder, the dimensions of the main nanopores which was in the range of 0.2 to 5 nm. Nanoporous powder had the following physical and technical parameters:

1. Specific surface area (BET), m2/g1380
2. The total pore volume, cm3/g1,42
3. The volume of the nanopores, cm3/g0,98
4. The amount of transient pores, cm3/g0,2
5. Ash content, not more %0,5
6. Bulk density, g/cm30,56

The average particle size of nanoporous carbon powder was set to about 30 micrometers. Nanoporous filter (9) was applied on the basis of the above NPCs powder. The thickness of the nanoporous filter comprised of 2.23 mm, and a density of 0.68 g/cm3. The mass content of nanoporous carbon in the filter material was 90%.

To study the effectiveness of separation of salts of transition elements was made of a mixed aqueous solution of the chlorides of Nickel and chromium in a quantity of 50 ml (concentration CrCl3and NiCl2about 1 wt.%). Used hydrated dichloride NiCl2·6H2O and chloride chromium CrCl3mark "H". Mass fraction of the main substances chloride NiCl2·6H2O and CrCl3not less than 97% and 98%, respectively. The molar ratio of the content of chromium and Nickel in solution was 1/1,2. The resulting solution was divided into two parts, 25 ml of the First part of the solution served as a reference (initial solution) to compare the ratio of the concentrations of the elements Ni and Cr with the corresponding parameter is m solution after selective separation.

Nanoporous powder (7) weighing 30 grams was placed in a working volume (8) installation (1). Later in the working volume of the installation was bathed in a mixed solution of chloride NiCl2+CrCl3in the amount of 25 ml After 50 minutes of exposure the working volume of the installation was subjected to vacuum for 40 minutes at a pressure of 10 mm Hg column. Since the specific total volume of nanopores NPC powder is 0.98 cm3/g, it is easy to see that after the evacuation of the installation of the entire solution is almost in nanopores NPC powder. Immediately after the degassing device (1), the pressure P of the air quantity 3 of the atmosphere through the pressure fitting (5) from the output fitting (6) device was replaced by a solution of nanopores NPC powder, in an amount of 10 ml for 15 minutes. Our research has shown that the gas pressure is mostly replaced by the solution of the relatively large nanopores carbon powder, and the main part of the residual solution (15 ml) after displacement remains in nanopores with relatively smaller sizes.

To study the effectiveness of the process of displacement solution of the nanopores NPC powder directly after the first process of displacement of working solution volume (8) installation (1) was filled with distilled water in an amount of 100 ml this was followed by a second process of displacement of the pressure solution is m the air. This procedure was repeated 10 times. With the aim of increasing concentrations of the investigated ions in overset the mortar after each process of displacement, as well as to increase the accuracy of optical measurements, the concentration of the investigated transition elements overset solution was grown by slow evaporation at 60°C.

For detailed research and management process for selective separation of a mixed aqueous solution of chlorides, was measured spectra of optical absorption overset solutions all 10 processes. Also for the accurate identification of the absorption spectra overset solutions was measured spectra of the test aqueous solutions of chloride NiCl2, CrCl3and NiCl2+CrCl3in the spectral range 200-1000 nm. For preparation of test solutions NiCl2and CrCl3we've taken the chloride NiCl2·6H2O and CrCl3in the amount of 0.5 grams and dissolved, each in 50 ml distilled water (concentration of NiCl2and CrCl3in the respective solutions 0,04208 M and 0,06316 M, respectively). Test mixed solution of NiCl2+CrCl3were prepared by mixing 2 ml of the prepared test solutions of chlorides of chromium and Nickel (concentration NiCl2and CrCl3in solution 0,021 M and 0,0325 M, respectively).

Measurements of the spectra of choice for the definition of absorption of aqueous solutions of NiCl 2, CrCl3mixtures of NiCl2+CrCl3and overset solution was carried on the spectrophotometer SF-2000 and Genesys-2 in the wavelength range 200-1000 nm. Used cell K-10 from the optical quartz. Measure all of the spectra were performed at room temperature. Thus the absorption of aqueous solutions were measured relative to water absorption and absorption of acidic solutions with respect to air. The selectivity of separation of the chlorides of Nickel and chromium was determined by elemental analysis of the dry residues of the original and the displaced solutions obtained by thermal evaporation at a temperature of 60°C in vacuum, by the method of x-ray fluorescence spectroscopy x-ray fluorescence spectrometer VRA-30.

Measurement of optical absorption of the original 1% water rastrera and solution after the first process of displacement solution of the nanopores NPC powder showed that after the first process of replacement of part of the absorption spectrum overset solution in the wavelength range 200-1000 nm is significantly different from the composition of the spectrum of the initial solution (Figure 5). In this case, as can be seen from the figure, increasing the number of processes of displacement practically does not change the spectral composition of the absorption of expelled fluids. In order to accurately identify the bands of the absorption spectrum of 1% aqueous solution of the chlorides of Nickel and chromium, as well as on what I determine the elemental composition of the extruded solution, conducted a detailed study of the absorption spectra of the test solutions of chloride NiCl2, CrCl3and NiCl2+CrCl3.

The Figure 6 shows the absorption spectra of the test aqueous solutions of chloride NiCl2, CrCl3and NiCl2+CrCl3. As can be seen from this figure, in the absorption spectrum of the test solution NiCl2in the wavelength range 200-1000 nm is observed intense absorption band with a maximum at 394 nm and a broad absorption band with two peaks 656 and 722 nm. From the literature [4] it is known that optical absorption spectra of an aqueous solution of Nickel dichloride observed transitions3A2g2Å2g,3A2g1Eg,3A2g3T1gand3A2g3T1g(P) with highs of pages: 1176; 658; 725 and 395 nm. From these results it follows that the absorption band with maximum at 394 nm (6) an aqueous solution of Nickel dichloride caused resolved in spin transition3A2g3T1g(P) of hydrated divalent ion. The absorption band in the region of wavelengths of 500-900 nm has a rather complicated form. This band is due to resolved in spin transition3A2g3T1g(maximum 722 nm) and Smoking in spin transitions3A2g1Egand3 A2g1T2g(maximum of 656 nm).

Absorption spectra of hydrated ions of trivalent chromiumhave bands with maxima 667, 575, 407 and 265 nm [4], which is caused by transitions4A2g2T2g,2E2g,4A2g4T2g,4A2g4T1g(F) and4A2g4T1g(F), respectively. As can be seen from the results of optical absorption test an aqueous solution of trichloride chromium CrCl3in the wavelength range 200-1000 nm in the absorption spectrum is dominated by two intense absorption bands with the maxima at 420 nm and 593 nm (6). In absorption spectrum is also observed weak band with maximum at 683 nm.

It is well known that the heat and the change of concentration of solutions of salts of trivalent chromium leads to the formation of isomeric hydrate complex. This process is accompanied by a strong change of the absorption spectra of salts of Cr (III), i.e. the absorption spectra of the solutions of trivalent chromium is strongly dependent on temperature [5] and the concentration of the solution. The analysis of the spectra of the test aqueous solution of trichloride chromium CrCl3showed that the absorption bands with the maxima at 420, 593 and 683 nm due to transitions4A2g4T1g(F)4A2g4T2g and4A2g2T2g,2E2grespectively.

Note that the shifts of the absorption maxima of the bands 420, 593 and 683 nm, compared with literature values (407, 575 and 667 nm) at 25°C, associated with low temperature (20°C) measurement of the spectra, as well as with the low concentration of chromium ions in the test solution.

Thus, as follows from the absorption spectra of the test aqueous solutions NiCl2, CrCl3and NiCl2+CrCl3the absorption band of the hydrated divalent ionsin the range of 350-500 nm overlaps with the absorption band (420 nm) of ions of trivalent chromium. Also the absorption band of 593 nm, due to ionsin the range of 500-750 nm has a partial overlap with the absorption broad band with two peaks 656 nm and 722 nm ions of divalent Nickel. Since the absorption band of 420 nm and 593 nm ionsin aqueous solution have significant overlap with the absorption bandsit is obvious that the method of optical absorption will not allow with sufficient accuracy to determine the ratio of ion concentrations of Nickel and chromium in mixed solutions. However, the method of optical absorption allows you to make quick and qualitative assessment of the changes in the concentrations of ions nick who I am and chromium in the mixed solution.

Figure 5 shows the absorption spectrum of 1% mixed source of an aqueous solution of chloride NiCl2+CrCl3in the spectral range 200-1000 nm. As can be seen from this figure, the absorption spectrum of the mixed solution has a complex shape with three maxima at wavelengths of 400 nm, 586 nm and 726 nm. It is obvious that the absorption band at 400 nm and 726 nm are mainly with hydrated divalent Nickel ionsand the absorption band of 586 nm - hydrated trivalent chromium ions. Moreover, we note that a small shift of the maxima of these bandsandcompared with the positions of the maxima of the respective bands of aqueous solutions of NiCl2and CrCl3connected, as indicated above, with a partial overlap of absorption bandsandin the mixed solution.

Analysis of the absorption spectra of 1% of a mixed aqueous solution of NiCl2+CrCl3after each displacement of the nanopores NPC powder shows that in the spectral range 200-1000 nm in the spectra occur only absorption band at 394 nm and a broad band in the long wavelength region with two peaks (656 nm 722 nm). The band with the maximum at 400 nm of the original 1% aqueous solution of NiCl2+CrCl3after ousting heterogeneous narrows, the maximum of the wasps is shifted in wavelength region and coincides with the maximum (394 nm) absorption bands of divalent Nickel. Narrowing and shift of the band of 400 nm associated with the absence in the spectrum of the absorption band of 420 nm, which is due to trivalent chromium ions. Detailed analysis shows that the parameters of the absorption spectra of aqueous solution of NiCl2and a mixed aqueous solution of NiCl2+CrCl3after displacement of the nanopores NPC powder is almost the same.

Elemental analysis of solids Kiddle 1% mixed solution of NiCl2+CrCl3received after tenfold displacement solution of the nanopores NPC-powder method x-ray fluorescence spectroscopy showed that the molar content of chromium and Nickel in the Kiddle is 1/1347. Since the molar content of chromium and Nickel in the original solution was 1/1,2, it is obvious that the proposed method for the extraction of Nickel dichloride from mixed aqueous solution of the chlorides of Nickel and chromium using nanoporous carbon material has a very high selectivity.

Example 2. This example illustrates the selectivity of the separation process of transition elements of the three-component aqueous solution of chlorides. For the selective separation was made of a mixed aqueous solution of the chlorides of Nickel, cobalt and chromium in a quantity of 50 ml (estimated concentration CrCl3, CoCl2and NiCl2about 1 wt.%). In the preparation of the solution was used guide datirovanie dichloride NiCl 2·6H2O, CoCl2·6H2O and trichloride CrCl3mark "H". Mass fraction of the main substances chloride NiCl2·6H2O CrCl3and CoCl·6H2O not less than 97%, 98% and 98%, respectively. The molar ratio of the content of chromium, Nickel and cobalt in solution was 1/1,2/1,2. The resulting solution was divided into two parts, 25 ml of the First part of the solution served as a reference (initial solution) to measure the absorption spectrum and conducting elemental analysis, and the second part for the selective separation. To increase the accuracy of identification of the spectra and determine the elemental composition of a mixed aqueous solution of chloride NiCl2+CoCl2+CrCl3also was investigated absorption spectrum of the test aqueous solution of cobalt dichloride CoCl2in the spectral range 200-1000 nm. For the preparation of the test aqueous solution of CoCl2hydrated dichloride CoCl2·6H2O weighing 0.5 g was dissolved in 10 ml distilled water (concentration of 0.21 M).

The process of selective separation of ternary aqueous solution of the chlorides of Nickel, chromium and cobalt were conducted under similar conditions described in example 1, using nanoporous carbon powder (7) in an amount of 35 grams. The duration of exposure under normal conditions, after pouring the solution in a work about JEM installation (1) and vacuum was 50 and 30 minutes, respectively. Conducted five processes of displacement solution from the pores of the NPC powder pressure of 3.5 atmospheres clean and dry air. The duration of each process of displacement was 12 minutes. Measured optical absorption of five overset solutions.

Measurement and analysis of the absorption spectra in the range 200-1000 nm 1% of the original mixed aqueous solution of CoCl2+NiCl2+CrCl3and overset solutions obtained after each process (5 processes) displacement of nanopores NPC powder showed that the spectra overset solutions appear only absorption band at 394 nm and inhomogeneous broadening of the band with maximum at 513 nm (Fig.7). The absorption band with maximum at 513 nm is formed by a partial overlap of the absorption bands 504 nm ionsand strip 394 nm ions. That is, according to the optical absorption spectra in the spectra of all five overset solutions almost no ion complexes of chromium.

For analysis of the process of selective separation of ternary aqueous solution of the chlorides of Nickel, chromium and cobalt, as well as to demonstrate the high selectivity of the extraction of compounds of transition elements of multicomponent solutions of the proposed method was carried out detailed studies of the test aqueous solutions of the components is of loredo NiCl 2, CrCl3(example 1), CoCl2and three-component aqueous solution of CoCl2+NiCl2+CrCl3.

Analysis of the absorption spectra of the test aqueous solutions of chloride CoCl2, NiCl2, CrCl3and CoCl2+NiCl2+CrCl3in the spectral range 200-1000 nm shows that in the absorption spectra of the solution CrCl3in the range 300-800 nm there are two broad bands with maxima at 422 nm and 596 nm (Fig). Broad band absorption spectrum of 1% aqueous solution of chlorides of transition elements Ni, Co and Cr (7) has four clearly pronounced maximum (398, 529, 593 and 734 nm). When this band with maximum at 398 nm is formed by an overlap of absorption bands of hydrated ionsand. Low-intensity absorption bands with maxima 593 nm and 734 nm is due to hydrated ionsandrespectively.

From numerous studies it is well known that in the absorption spectra of aqueous solution of hydrated divalent cobaltthere are the following three transition4T1g4T2g,4T1g4A2gand4T1g4T1g(P) [4]. The intensity of the absorption transition4T2g4T1gbecome six-coordinated to the complex of cobalt (II) has a maximum at a wavelength of 1235 nm, and the intensity of the transition4T1g4T1g(P) 515 nm. The absorption transition4T1g4A2g(625 nm) has a very low value and rarely manifests itself clearly. As can be seen from figure 8, in the wave length range 200-1000 nm absorption spectrum of 0.21 M test aqueous solution of CoCl2at room temperature has the form of a broad band with a maximum of 504 nm. Note that the absorption spectra of aqueous solution of CoCl2significantly depend on the degree of hydration of divalent cobalt ions. In addition, the position of the band maximum transition4T1g4T1g(P) (515 nm) complexdepends on the temperature and concentration of cobalt in solution. Our research and detailed analysis of the absorption spectra of aqueous solutions of cobalt dichloride different concentrations showed that the band with the maximum 529 nm 1% three-component aqueous solution of CoCl2+NiCl2+CrCl3associated with hydrated ions.

Comparison of parameters of the spectra of the initial solution of CoCl2+NiCl2+CrCl3and the solution obtained immediately after the first process of displacement of the nanopores of nanoporous carbon powder, you can see that the width of the strip 398 nm significantly reduces the I. While the band maximum 398 nm is shifted to shorter wavelengths and coincides with the maximum bandwidth (394 nm) absorption of hydrated become six-coordinated Nickel ions. Narrowing and shift of the indicated absorption bands overset solution associated with the absence of its spectrum absorption band 593 nm, due to the hydrated chromium ions. That is, increasing the number of processes of displacement reduces the concentration of ionic complexes of chromium in overset solution.

Elemental analysis of solids superseded by the three-component solution obtained after five displacement solution of the nanopores NPC-powder method x-ray fluorescence spectroscopy showed that the molar content of chromium, Nickel and cobalt in overset solution is 1/715/865. Considering the fact that the molar content of chromium, Nickel and cobalt in the initial solution was 1/1,2/1,2, from these results it follows that the efficiency of extraction of hydrated ions of chromium, Nickel and cobalt from the nanopores powder differ significantly. The efficiency of extraction of trivalent chromium ions in 865 times and 715 times lower than the corresponding parameters of the divalent ions of cobalt and Nickel, respectively. Thus the displacement efficiency of cobalt ions 1.2 times the displacement efficiency of Nickel.

Thus, research is the development and analysis of optical properties, as well as measurement of the elemental content of the extruded aqueous solution of CoCl2+NiCl2+CrCl3show that in contrast to ions of cobalt and Nickel, the main part of the chromium ions remains in nanoporous carbon powder after displacement solution. From this example it is obvious that the low recovery efficiency hydrated trivalent chromium ions from nanopores NPC powder will allow you to use the proposed method to obtain chromium, Nickel and cobalt in industrial quantities from a variety of multicomponent solutions. It is also clear that the use of cascading extraction process will allow you to obtain a salt of chromium, Nickel, cobalt and other transition elements of high purity.

Example 3. This example demonstrates the ability of selective extraction of chlorides of titanium and Nickel from their mixed aqueous solution of the proposed method. With the aim of studying the spectra of chlorides TiCl3, NiCl2and TiCl3+NiCl2made of 1.5% solution of the above chloride. For the preparation of solutions used hydrated dichloride NiCl2·6H2O mark "H" and a 15% solution of trichloride titanium TiCl3a 10% aqueous solution of hydrochloric acid. Mass fraction of the main substances dichloride Nickel NiCl2·6N2Of not less than 97%.

Test a 1.5% solution of TiCl3was p is gotovlen by dissolving 5 ml of 15% solution of trichloride titanium in distilled water 50 ml That is, the specified solvent solution contains 99% N2About 1% HCl. Aqueous solution with 1.5% of the estimated concentration of Nickel dichloride was made by dissolving hydrated dichloride NiCl2·6H2O mass 1,375 grams in distilled water with a volume of 50 ml.

A mixed solution of 50 ml containing 1.5% of TiCl3and 1.5% NiCl2for carrying out the selective extraction of chlorides of Nickel and titanium were prepared by mixing 25 ml of 3% solution of TiCl3(solvent - 2% HCl+98% N2O) and 25 ml of 3% aqueous solution of Nickel dichloride. Obviously, the solvent of the mixed solution contains 99% N2About 1% HCl. The obtained mixed solution was divided into two parts, 25 ml of the First and second parts of the solution were used, respectively, to measure the optical spectra and elemental composition of the initial solution and the selective extraction of chlorides of Nickel and titanium from the solution.

Process for selective separation of a two component aqueous solution of the chlorides of titanium and Nickel were carried out under similar conditions described in example 1. Used nanoporous carbon powder (7) in an amount of 30 grams and 1.5% solution of the chlorides of titanium and Nickel in the amount of 25 ml. of shutter speed under normal conditions, after pouring the solution in the working volume (8) of the device (1) and vacuum costal is whether 60 and 30 minutes, respectively. It was further held the first process of displacement solution. Directly after the first process of displacement of the solution, working volume (8) of the device (1) was filled with distilled water in an amount of 100 ml After 30-minute exposure was carried out a second process of displacement solution. This procedure was carried out three times. All four of the process of displacement solution of the nanopores NPC powder was carried out by pressure of 2.8 atmosphere clean and dry air. The duration of each process of displacement was 14 minutes. Measured optical absorption replaced all four solutions.

After the fourth process of displacement of the solution were extracted from the nanopores NPC powder remaining in nanopores ion complexes of titanium and Nickel, according to the proposed method. For this purpose, in the working volume (8) of the device (1) was filled with highly concentrated (37%) aqueous solution of hydrochloric acid in 30 ml of the Process of extracting residual complexes of titanium and Nickel from nanopores NPC powder was repeated two times, the pressure of 3.2 atmospheres clean and dry air. For each extraction process was used 37% solution of hydrochloric acid. After the first extraction process was carried out measurement of the optical absorption spectrum of the obtained solution of hydrochloric acid. After the second extraction process is possible the resulting hydrochloric acid solution was mixed with a solution of the first displacement. With the purpose of increase in solution concentration extracted from the nanopore ion complexes was conducted evaporation of the solution at a temperature of 80°C.

For the elemental analysis of the solids of the original, replaced and removed from the nanopores NPC-powder solutions were obtained by thermal evaporation of the solution at a temperature of 60°C in vacuum and then by calcination at a temperature of 950°C. X-ray fluorescence analysis was performed on x-ray fluorescence spectrometer "AXIOS Advanced".

Studies of the optical absorption spectra of all four displaced fluids in the wavelength range 200-1100 nm (Figure 9) showed that the parameters and structure of the absorption spectrum of the four evicted solutions in the field of wavelengths 200-1100 nm significantly differ from the parameters and composition of the source spectrum of the mixed solution. In particular, the absorption spectra of the four evicted solutions there is no intense absorption band with maximum at 503 nm, which is present in the range of the initial solution and, as will be shown below, caused by the absorption of ionic complex of trivalent titanium. Also note that the parameters of all the displaced fluids in the wavelength range 200-360 nm significantly differ from the parameters of the corresponding region of the spectrum of the original mixed solution (Fig.9, spectrum 1). If with decreasing wavelength in diapazone 360 nm absorption source solution increases from 340 nm, the initial solution absorption growth begins with a wavelength of 360 nm. From spectral studies indicate that overset solutions of ionic complexes of titanium is practically absent. That is, after the first process of displacement of solution ionic complexes of titanium, in the main, remain localized in nanoporous carbon material, and ion complexes of Nickel pass from nanopores in overset solution.

For detailed analysis of the process of selective extraction of both components of a two-component solution of the chlorides of titanium and Nickel were conducted detailed research and analysis of the optical spectra of the test solutions of titanium chloride and a mixed solution of chlorides of titanium and Nickel (detailed analysis of the spectra of an aqueous solution of Nickel chloride described in example 1). Ionic complexes of trivalent titanium and numerous ion complexes of various transition elements in solutions are become six-coordinated complexes with different dipole moments. Therefore, a detailed study and analysis of the spectra of the above solutions are also aimed at demonstrating the wide possibilities of the proposed method for the selective extraction of salts of various transition elements of multicomponent solutions.

Figure 10 shows the absorption spectra of the test of 1.5% aqueous solutions of chlorides iCl 2, TiCl3and NiCl2+TiCl3in the spectral range 200-1100 nm. As can be seen from this figure (spectrum 2), in the absorption spectrum of the test solution TiCl3in the wavelength range 200-1100 nm is observed intense absorption band with maximum at 503 nm (19881 cm-1) and a weak band (or, as often called, shoulder) absorption with a maximum 582 nm (17181 cm-1). These absorption bands due to the intracenter population transitions 3d-3d trivalent ion titanium Ti3+. The absorption band with a maximum 977 nm solution of TiCl3associated with water absorption (11, lane 975 nm spectrum 1). Note that when the 700-1200 nm absorption spectra of aqueous solutions, there are absorption bands of salts of transition elements, the position of the strip 975 nm in the spectra is shifted. Depending on the spectral position of the absorption bands of the transition elements of the band maximum 975 nm is shifted to longer or shorter wavelengths. For example, as can be seen from figure 10, the maximum absorption band of water (975 nm) in aqueous solution of TiCl3is shifted to the value of 977 nm, and in the solution of NiCl2- 985 nm.

From the literature it is well known [4]that in the optical spectra become six-coordinated complex of trivalent titaniumdominated by an intense absorption band with a maximum 20100 cm-1(497,5 nm) and SL is the fight the shoulder of absorption with a maximum 17400 cm -1(574,7 nm). In addition to complexalso characteristic absorption band is observed in most other complexes of titanium Ti(III) with coordination number 6, which usually have a purple color. In the above compounds of trivalent ion titanium Ti3+has the electronic configuration 3d1. The fivefold degenerate term2D configuration 3d1free ion Ti3+in octahedral ligand field become six-coordinated complex of Oh(Fig) is split into levels2T2g(ground state) and2Egas shown in Fig.12b.

Many become six-coordinated complexes of trivalent titanium with electronic configuration 3d1there is often a Jahn-teller effect, which leads to axial distortion of the symmetry of the ion complexes and, consequently, the splitting of the degenerate levels [4, 6]. Typically, the Jahn-teller effect is more strongly observed in terms than the terms So the magnitude of the splitting level2Egto become six-coordinated complexes of trivalent titanium is in the range 1000-4500 cm-1and level2T2g- in the range of 420-800 cm-1. Various researchers have theoretically and experimentally demonstrated that the presence of a shoulder absorption (574,7 nm) transition2T2g2Egthree the aqueous octahedral complex titanium associated with the Jahn-teller splitting of the excited state of2Eg(Fig.12b). Thus, according to literature data, the magnitude of the splitting level2Egcomplexis 2700 cm-1. The results of the above analysis show that the optical absorption spectrum of solutions with complex titaniumallows you to accurately identify the presence of solutions of trivalent titanium ion.

As can be seen from the absorption spectrum of the test solution TiCl3(Figure 10), the maximum absorption band (503 nm) transition2T2g2Egion complexshifted to lower energies at 220 cm-1compared to the maximum of the absorption band (497,5 nm) complexin aqueous solution. Detailed analysis of the experimental results of studies of the optical spectra of TiCl3in various solutions shows that the magnitude of the splitting of the term2D complexto a certain extent depends on the composition and properties of the solvent. Our studies of the spectra of complexesin aqueous hydrochloric acid solution with different concentrations showed that the position of the band maximum transition2T2g2Egto the complex depends on the concentration of hydrochloric acid. For example, when the concentration of the hydrochloric acid 10% solution of the position of the maximum2T2g2Egthe transition is at a wavelength of 510 nm. Experimentally it was found that with decreasing concentration of hydrochloric acid in solution, the band maximum is shifted to shorter wavelengths. When the concentration of hydrochloric acid 1% of the maximum of the absorption band is at a wavelength of 503 nm. It is also important to note that the magnitude of the splitting of the excited level2Egcomplexdue to the Jahn-teller effect, in the range of concentration of hydrochloric acid 1-10% is almost not dependent on the concentration of hydrated chloride ions, and in the specified range of concentration of HCl is 2700 cm-1. As will be shown below, the magnitude of the Jahn-teller splitting is greatly increased at high concentrations of hydrochloric acid.

theoretical analysis allows to make the following important assumption is the shift of the maximum absorption band of the transition2T2g2Egin the region of long wavelengths, when the concentration of hydrochloric acid in aqueous solution TiCl3associated with the interaction of hydrated chloride ions with complextrivalent titanium. Because the change of conc the AI HCl in aqueous solution is not accompanied by a change in the value of the splitting level of the excited state of 2Egcomplexthen, it is obvious that the complex interactionwith hydrated ions of chlorine does not reduce the symmetry of hydrated ionic complex of titanium.

In example 1 it was shown that in the wavelength range 200-1000 nm in the absorption spectrum of hydrated divalent ionin aqueous solution observed intense absorption band with a maximum at 394 nm and a broad absorption band with two peaks 656 and 722 nm. Now consider the features of the optical spectra NiCl2and TiCl2in aqueous hydrochloric acid solutions of different concentrations. As can be seen from Tiga, the maximum absorption band of the transition2T2g2Egcomplexdepends on the concentration of hydrochloric acid. When the concentration of hydrochloric acid in aqueous solution 1%, 5%, 10% and 37%, the position of the maximum absorption band of the above passage is, accordingly, 503, 505, 510, and 512 nm. The experimental results show a strong and inhomogeneous broadening of the absorption bands of the transition2T2g2Egwhen the concentration of hydrochloric acid 37% (Figa). The value of the Jahn-teller splitting of the excited state of2Egsignificantly grows from 2700 cm-1up to 4 933 cm .

Thus, at high concentration of hydrochloric acid the maximum absorption band of the transition2T2g2Egshifts in the region of long wavelengths at 349 cm-1(43 MeV)and Jahn-teller splitting of the excited state increases to values 4933 cm-1(611 MeV). The appearance of a new absorption band in the spectrum of the complexdue to increased Jahn-teller effect, which consequently enhances the splitting of the ground state2T2gion titanium. Detailed analysis of the absorption spectra of the complexin aqueous solution with different concentration of hydrochloric acid shows that the decrease in the energy transition2T2g2Egwith increasing concentration of acid in the solution is due mainly to the increased interaction of hydrated chloride ions with complex.

This interaction increases the distance of the water molecules and the Central ion titanium octahedral complex (Figa). That is, with increasing concentration of hydrochloric acid in the solution trichloride titanium grow the size of hydrated complex.

Note that, as is well known, salts of many transition metals at low concentrations of hydrochloric acid are water connections, and when Bo is its high concentration of acid chloride ions displace water molecules hydrated complex of the metal. In this case, the composition of the hydrated complex of the metal M is changed with the following sequence:

.

This circumstance will change size, symmetry and growth of the dipole moments of hydrated complexes of metals that will facilitate the process of extracting ion complexes of nanopores nanoporous material.

In contrast to the absorption band of the complexthe position of the absorption bands of the transition3A2g3T1g(P) complex(394 nm) in the range of concentration of hydrochloric acid 1%-10% is almost not dependent on the concentration of hydrated chloride ions (Fig), at room temperature the solution. These experimental results clearly indicate that the secondary shell of the hydrated chloride ions at a low concentration has a strong influence on the parameters of the complexand virtually no effect on the parameters of the complexdivalent Nickel. It is also clear that in the specified range hydrochloric acid water molecules complexreplaced by chlorine ions.

From Fig follows that at high concentration (37%) hydrochloric acid spectral parameters complexchange. The maximum of the wasps absorption transition 3A2g3T1g(P) is shifted to longer wavelengths and is 419 nm. Also significantly change the parameters of the long-wave absorption band with two peaks 656 and 722 nm. First, the long-wavelength absorption band is divided into three distinct peak (678, 700 and 774 nm). The maximum of the main absorption band 722 nm is shifted to the long wavelength region of the spectrum and is 774 nm. Secondly, two long-wavelength absorption band is widened heterogeneous and splits, a new absorption band with a weak intensity. It is obvious that at high concentration of hydrochloric acid is significant distortion of the structure or change in the composition of the complexthat leads to the reduction of symmetry and the change in the absorption spectrum of the latter. From the above analysis it follows that the high sensitivity of the parameters of the ion complexes to external influences creates favorable conditions for their penetration into the nanopores with different sizes, strong hold complexes in nanopores and to displace complexes of nanopores nanoporous material.

Elemental analysis method x-ray fluorescence spectroscopy of solids, 1.5% of the original aqueous solution of chlorides TiCl3+NiCl2showed that the mass content of Ni, TiO2and Cl in ostad the initial solution is, accordingly, 3,79/3.46 in/1.0 in. That is, in the initial solution, the mass of Nickel in 1,828 times the weight of the titanium. The results of elemental analysis of solids mixed ousted four solutions of nanopores NPC powder showed that the mass content of Ni, TiO2and Cl in the dry residue ranges, respectively, 2,085/0,117/1.0 in. It is obvious that the mass of Nickel in overset solution 29.7 times the weight of the titanium. Considering the fact that the mass of the Nickel content in the initial solution in 1,828 times the weight of titanium, after four displacement of the mass ratio of Nickel and titanium is growing more than 16 times, which demonstrates the high selectivity of the separation process of the proposed method.

Elemental analysis of solids concentrated hydrochloric acid after extraction, the residual ion complexes of nanopores showed that the mass content of Ni, TiO2and Cl in the specified balance is, accordingly, 0,854/45,57/1.0 in. From these data it follows that the mass of titanium in the dry residue is extracted from the nanopores NPC powder about 32 times the weight of Nickel. These results demonstrate the high degree of selectivity of separation of the chlorides of titanium and Nickel, and show that after four displacement of the nanopores of the mixed solution in nanopores remains largely chloride titanium.

Thus, the results of mass analysis of the su is their residues and optical absorption solutions reliably show a high selectivity of the extraction process of the chlorides of titanium and Nickel using NPC-powder. The mass ratio of Nickel and titanium in overset solution is, respectively, 1,828 and 29.7, and the solution after the extraction of residual chlorides of titanium and Nickel from nanopores NPC-powder - 0,03126. From the obtained results, it is obvious that increasing the number of processes of displacement of the mixed solution of the nanopores of the carbon powder will significantly increase the selectivity of the separation.

Example 4. This example shows the process of introducing ion complexes in the nanopores of nanoporous carbon material and extraction complexes of nanopores using a polarization potential of the EDL nanoporous material according to the proposed method. These processes have been carried out using a two-electrode electrochemical cell (EC) with the design shown in Fig.

In the EU-the cell (11) were used coal plate (12) in a quantity of 5 with the dimensions of 60×48×2.2 mm3. Coal plate was made on the basis of nanoporous carbon powder, with those specified in example 1 parameters, and a binder material PTFE. The mass content of nanoporous carbon material carbon plate (12) was 90%. The total mass, electrical resistivity and density of the coal plates EU-cells (11) had a value, respectively, of 2.15 Ohm·cm, 0,606 g/cm3and 19.2, collect the R current (13) electrode of coal plates (12) cells (11) and the counter-electrode (14) were used from saturated furan polymer material Grafoil with the dimensions of 120×48×0.3 mm 3. For the separation electrode cell was used porous polypropylene separator (15) type PP-7B thickness of 100 μm. The electrode blocks of the cell was housed in a housing (16) of polyethylene. After fabrication of the cell she was placed in a special device, which provided a uniform pressure (0.5 kg/cm2) on the electrodes of the EU-cells, to ensure reliable contact of the coal plates, collector current (13). To measure potentials of coal plates and counter-electrode cell was installed reference electrode (17) Ag/AgCl with a standard potential 0,201 Century

To fill the cells of the investigated solutions of (18) conclusions collector current coal plates and counter-electrode joined to the input terminals of the respective channels of the multichannel measurement system. Collector current (13), coal plates EU-cells was attached to the positive pole of the input of the measuring system, and the output of the counter-electrode (14) and reference electrode (17) to the negative pole, for a detailed study of the kinetics of the potential of coal plates when filling the nanopores test solution.

As an important point when filled with electrolyte cell is the behavior of the potential coal plates, the cells were quickly filled a 1.5% solution (18) trichloride titanium TiCl3(solvent - water 99%, Solanaceae 1%) in a few minutes after switching on the measuring setup. The cell was filled with a solution of 25 ml. Voltage and the potentials of the electrodes of the EU-cells were recorded continuously to stabilize them (Fig).

As seen on Fig, the voltage U of the cell immediately after pouring the solution is monotonically increasing and after 5 hours reaches the maximum value (0,56). Later in the time range 5-32 hours voltage monotonically decreases to 0.4 V, and after 32 hours there is a sharp increase in the rate of voltage reduction to 0.04 Century, the Average speed reduction of voltage in the range of 5-32 32-45 hours and hours respectively, of 5.9 mV/hour and 27.7 mV/hour. The potential of coal plates & Phi;CPEU-cells early after pouring the solution slowly increases and then remains virtually unchanged during long-term storage. After 8 hours of storage cells the capacity of its coal plate reaches a value of 0.58 In (relative to SHE). The potential of the counter-electrode φGRafter pouring the solution is about minus 24 mV, and with increasing time slowly increasing. After 32 hours of storage cells, the growth rate of potential φGRincreases significantly. Note that during prolonged storage cell (not shown in Fig) the potential coal plates and counter-electrode to have the same value (about 0,58 V). The voltage U of the cell associated with the potentials of the coal plate & Phi;CFand protivoelektrodom the and φ GRthe formula U=φGR- ΦCP.

During storage of the EU-cells was visually observed that the free solution light purple cells gradually discolored. After 10 hours of storage the colour of the solution cell has practically disappeared. The study of the spectra of optical absorption flushed from the cell solution after 55 hours of storage (Fig) showed that the spectrum of the merged solution (spectrum 2) differs significantly from the spectrum of the initial solution (spectrum 1). In the spectrum flushed from the cell solution is completely absent absorption band ferric complex of titanium. This increases the absorption solution in the range 200-480 nm. From these results it is evident that ion complexes of titanium are in nanopores nanoporous carbon material.

After completion of the measurement of the kinetics and voltage potentials of the electrodes of the EU-cell-free solution from the cell was completely Slipi this note that part of the solution remains in nanopores coal plates. Next, the cell was filled with an aqueous solution of hydrochloric acid in 25 ml.

To extract ion complexes of titanium nanopores, after filling of the cell 37% aqueous solution of hydrochloric acid potential of coal plates were polarizable in the area of negative potential by a constant current of 50 mA for 2 hours. When 2-hour polarization application : is the value of the potential of coal plates were changed from the equilibrium value of 0.58 V to values minus of 0.12 In (relative to the potential SHE). Note that in the process of polarization visually it was noticeable that after an hour of polarization of the free solution of the cell gradually becomes light purple color. After two hours of polarization of the free solution cell was merged for the analysis of optical spectra.

The spectrum of optical absorption of the solution EU-cells (Fig, spectrum 3), after two hours of polarization of coal plates of the cell with a solution of hydrochloric acid, shows that the solution contains ionic complexes of trivalent titanium. In the spectrum of the observed absorption band with maximum at 465 nm, and a band of low intensity with maximum 641 nm, due to the splitting of the Jahn-teller effect. As can be seen from this spectrum, the maximum of the absorption band (465 nm) is shifted in the wavelength region of the spectrum at 1625 cm-1compared with a maximum bandwidth of 1.5% aqueous solution of trichloride titanium TiCl3(example 3). This Jahn-teller splitting of the excited state of the solvated complexes of trivalent ion titanium has grown considerably and is 5905 cm-1. A more detailed analysis of the spectra of the above solution allows to assume that the displacement of the nanopore ion complexes of titanium by polarization potential coal plates in the region of negative values leads to a significant change in the symmetry and composition of the as ion complexes.

Thus, this example clearly demonstrates the high efficiency of extraction of ionic complexes of nanopores nanoporous carbon plate by way of the polarization potential of the EDL nanoporous material in the opposite direction from the equilibrium value of the potential, according to the proposed method. Obviously, the performance and efficiency of extraction of ionic complexes of transition, rare earth and actinoid elements of the nanopores nanoporous plate depends on the structures of the electrochemical cell and its nanoporous electrode.

Example 5. For selective extraction of the aqueous components of salts of rare earth elements, according to the proposed method, in the form of salts of rare earth metals were selected sulfates neodymium and europium. Sulfate, europium Eu2(SO4)3was obtained by dissolving metallic europium brand computers-1 in sulfuric acid brand OFS and evaporation of the solution at a temperature of 180°C. To obtain crystalline Eu2(SO4)3·8H2O europium sulfate was dissolved in distilled water, the resulting solution was dried at 90°C.

For the manufacture of a solution with ions of Eu3+and Nd3+were used synthesized europium sulfate and sulfate nd Nd2(SO4)3·8H2O Mar and OFS. The solubility of sulfate europium Eu2(SO4)3·8H2O in 100 ml of distilled water at room temperature is of 2.56 grams and sulfate nd Nd2(SO4)3·8H2O - 8,87 grams. Therefore, to avoid precipitation used salts in solution and the occurrence of concentration effects in the preparation of aqueous solutions with ions of Eu3+and Nd3+the number of sulfates Eu2(SO4)3·8H2O and Nd2(SO4)3·8H2O in 50 ml water was 0.5 gram.

To obtain a mixed solution of chloride EuCl3+NdCl3in 50 ml of water were dissolved in 0.5 grams of hydrated sulfates europium and neodymium. The resulting solution was divided into two parts 30 ml and 20 ml of One part of the solution (30 ml) was used for selective extraction of components, and the second part as the test solution.

Selective extraction was carried out using a device (1)shown in figure 4. Used nanoporous carbon powder with those specified in example 1 parameters. Process for the selective extraction of sulphate of europium and neodymium were conducted under similar conditions described in example 1, using nanoporous carbon powder (7) in an amount of 30 grams. The duration of exposure under normal conditions, after casting, is of astora in the working volume of the unit (1) and vacuum was 30 and 20 minutes, respectively. At a pressure of pure nitrogen gas 4.5 atmospheres of nanopores nanoporous carbon powder was replaced by a solution of 22 ml for 15 minutes.

Directly after the first process of displacement of the working volume (7) of the device (1) filled with distilled water in an amount of 100 ml, and after 30-minute exposure, the eviction process was repeated at a pressure of 4.5 atmospheres. The extruded solution was filled in the working volume (7) of the device (1) and was subjected to repeated displacement under similar conditions. This procedure was repeated 10 times. Further, after the completion of the tenth process of displacement resulting solution was mixed with ousted in the first process solution (22 ml). With the aim of increasing the concentration of ions in solution and, consequently, the accuracy of the measurement of absorption spectra, the amount of solution was reduced to 10 ml by evaporation at 60°C.

Measurement of optical absorption test water solutions Eu2(SO4)3Nd2(SO4)3and mixtures thereof, and overset solution was performed on a spectrophotometer SF-2000 in the range of 200-1000 nm and 380-650 nm.

Measurement of optical absorption of aqueous solutions of sulfates Eu2(SO4)3Nd2(SO4)3and Eu2(SO4)3+Nd2(SO4)3showed that the range is not wavelength 200-1000 nm observed a number of narrow and intense absorption bands, associated with ions of neodymium, and one intense band due to europium ions. On Fig shows the spectra of these solutions in the wavelength range 380-650 where the absorption bands of hydrated ions of europium and neodymium. Note that the ionic complexes of Nd3+and Eu3+and ionic complexes of other rare earth elements, have a narrow absorption band, which is due to intracenter population transitions of 4f-4f. The shape and intensity of the absorption bands of hydrated ions [Nd(H2O)8]3+and [Eu(H2O)8]3+in aqueous solutions in a wide range of practically does not depend on the concentrations and types of ions in solution. This allows high accuracy to determine the content of ionic complexes of rare earth elements in solutions from the optical absorption spectra of solutions.

To determine the selectivity of the extraction from a solution of sulphate of neodymium and europium were calculated ratio of the concentrations of hydrated ions of neodymium and europium in the original and the displaced fluids. To calculate the concentration of hydrated ions of europium solution was used, the absorption band with maximum at 394 nm (transitions7Fa 0.1-5L6), and the concentration of hydrated ions of neodymium - absorption band with maximum at 576 nm (transitions4I9/2-2 G5/2,7/2). Note that the narrow absorption band maximum of 576 nm and 394 nm hydrated ions of neodymium and europium, respectively, have virtually no overlap with other absorption bands of these ions, which allows to calculate the ratio of neodymium ions and europium in the mixed solution with high accuracy.

On Fig shows the absorption spectra of the mixed source of an aqueous solution of sulphate of europium and neodymium, and overset solution. As can be seen from these spectra, the ratio of the intensities of absorption bands 576 nm and 394 nm source solution out of the solution differ significantly. Detailed calculations showed that the ratio of the concentration of neodymium ions and europium in overset solution 1.7 times more compared with the corresponding value of the initial solution. It is obvious that the coefficient of separation of neodymium and europium is at least 1.7. Because the dipole moments of the hydrated ion complexes almost all rare earth elements are different, the results clearly demonstrate the high selectivity of the extraction of rare earth elements using nanoporous carbon materials. It is also clear that the effectiveness of selective extraction of rare earth elements can be increased by narrowing the distribution of the nanopore size of the NAS is a porous material and a careful choice of the optimal modes extraction technology.

Literature

[1]. K.Hideko and .Hiroshi. Separation of Thallium and Gold on Activated Carbon, Analytical Sciences February, Vol.9 (1993).

[2]. S.A.Kazaryan, S.N.Razumov, S.V.Litvinenko, G.G.Kharisov, and V.I.Kogan. Mathematical Model of Heterogeneous Electrochemical Capacitors and Calculation of Their Parameters, J.Electrochem. Soc, Volume 153 (9), A1655-A1671 (2006).

[3]. .E.Conway, Electrochemical Supercapacitors, Scientific Fundamentals and Technological Applications, Kluwer Academic Plenum Publishers, New York, (1999).

[4]. Aliver. Electronic spectroscopy of inorganic compounds, Moscow, "Mir" (1987).

[5]. V.K.Garg and P.S.Relan. Kinetics of Substitution of Oxalato Ligands Tris (Oxalato) Cromate(III) Ions with 1,2-Ciclohexylene Dinitrilotetraacetic Acid(CDTA) in Aqueous Alkaline Media, PINSA 64. A, No.66, pp.747-751, November (1998).

[6]. Ibberson. Electronic structure and properties of coordination compounds, Leningrad, "Chemistry" (1986).

1. Process for the selective extraction of salts of transition, rare earth and actinoid elements of multicomponent acidic solutions containing ionic complexes of these elements, characterized in that exercise consistently
accommodation nanoporous conductive material in the working volume, the fill source solution filling the nanopores of the above-mentioned material solution for localization in nanopores material ion complex salt extracted by the electrostatic interaction of the dipole moment of the complex elements with the electric field of the electrical double layer boundary wall of the nanopores - solution",
the latter is out of the nanopores weakly localized in nanopores ion complexes of elements pressure gas or liquid,
filling the nanopores nanoporous conductive material with a solution of an inorganic acid and high concentrations of
extract from the nanopores of the residual ion complexes of elements pressure gas or liquid.

2. The method according to claim 1, characterized in that the use of a multicomponent solution containing separate salts of transition elements of the iron group, the group of palladium and platinum-group in which the dipole moments of the solvated ionic complexes of the above elements is non-zero.

3. The method according to claim 1, characterized in that the use of a multicomponent solution containing pure salt of rare-earth elements with atomic number Z=58-71 and actinoid elements with atomic number Z=90-94, in which the dipole moments of the solvated ionic complexes of the above elements is non-zero.

4. The method according to claim 1, characterized in that as nanoporous conductive material used nanoporous carbon conductive material or nanoporous material of the electroconductive titanium oxide, or nanoporous material titanium carbide, or mixtures thereof in various combinations.

5. The method according to claim 4, characterized in that the use of nanoporous material, the electrochemical potential of the electrical double layer which is positive relative to potentialtarget hydrogen reference electrode.

6. The method according to claim 4, characterized in that the use of nanoporous material with the size of the nanopores from 0.2 nm to 5 nm.

7. The method according to claim 4, characterized in that the use of the nanomaterial with a specific surface area of from 600 m2/g to 1800 m2/year

8. The method according to claim 4, characterized in that the use of nanoporous material with a specific pore volume of 0.5 cm3/g to 1.5 cm3/year

9. The method according to claim 4, characterized in that the use of nanoporous material with electrical resistivity of 0.01 Ω·cm to 1000 Ohms·see

10. The method according to claim 4, characterized in that the use of nanoporous conductive material in the form of powders or granules, or fibers, or plates, or disks.

11. The method according to claim 10, characterized in that the use of nanoporous materials made from nanoporous carbon powder and a polymeric binder materials.

12. The method according to claim 1, characterized in that the dielectric constant of the solvent multicomponent acidic solutions containing ionic complexes of these elements ranges from 25 to 100.

13. The method according to claim 1, characterized in that the filling of the nanopores nanoporous conductive material, the initial solution is conducted by mixing the aforementioned nanoporous material with the solution and the mixture was kept under normal conditions for a period of 1 hour to 20 hours

14. Spasibo 13, characterized in that the mixture of nanoporous material and the solution is subjected to vacuum for maximum filling of the pores of nanoporous material with a solution.

15. The method according to item 13, wherein the ratio of the volume of the solution to the total volume of pores of nanoporous material in the mixture is from 0.5 to 1.2.

16. The method according to claim 1, characterized in that the use of solutions having the length of the Debye shielding constituting from 0.2 nm to 200 nm.

17. The method according to claim 1, characterized in that the displacement of the nanopores weakly localized in nanopores ion complexes elements hold the pressure of the air or gaseous nitrogen or gaseous carbon dioxide, or water.

18. The method according to claim 1, characterized in that to fill the pores of nanoporous material inorganic acid of high concentration is used, the acid solution with a dielectric constant of not more than 20, in particular solutions of hydrochloric acid, sulfuric acid, phosphoric acid, hydrofluoric acid and mixtures thereof.

19. The method according to claim 1, characterized in that the extraction of the nanopores of the residual ion complexes of transition and/or rare earth and/or actinoid elements hold the pressure of the air or gaseous nitrogen or gaseous carbon dioxide, or water, or aqueous solutions of inorganic acids with dielectric pronice the spine of not more than 20.

20. The method according to claim 1, wherein the parameter is selected distribution of pore size nanoporous material and the length value of the Debye screening of multicomponent solution for selective extraction of salt each transition, or rare earth or actinoid elements.

21. Process for the selective extraction of salts of transition metals, rare-earth or actinoid elements of multicomponent acidic solutions containing ionic complexes of these elements, characterized in that exercise consistently
the placement of the polarizable electrode of electric double-layer-based nanoporous conductive material in the electrochemical cell, comprising a housing, a counter-electrode, a porous separator separating the electrodes of the cell
fill the housing of the electrochemical cell with a solution containing ionic complexes of these elements,
filling the nanopores of the mentioned electrode cell with a solution for the localization of ion complexes in the volume of nanopores nanoporous material by the electrostatic interaction of the dipole moment of the complex elements with the electric field of the electrical double layer boundary wall of the nanopores - solution" of the electrodes of the cell
eviction from the housing of the electrochemical cell solution pressure gases Il the liquids,
fill the housing of the electrochemical cell inorganic acid and high concentrations of
extract from the nanopores of the residual ion complexes of elements by the polarization potential of the electrical double layer of the polarizable electrode electrochemical cell.

22. The method according to item 21, wherein the use of a multicomponent solution containing separate salts of transition elements of the iron group, the group of palladium and platinum-group in which the dipole moments of the solvated ionic complexes of the above elements is non-zero.

23. The method according to item 21, wherein the use of a multicomponent solution containing pure salt of rare-earth elements with atomic number Z=58-71 and actinoid elements with atomic number Z=90-94, in which the dipole moments of the solvated ionic complexes of the above elements is non-zero.

24. The method according to item 21, wherein as the conductive nanoporous material using nanoporous carbon conductive material or nanoporous material of the electroconductive titanium oxide, or nanoporous material titanium carbide, or a mixture of different with different combinations.

25. The method according to item 21, wherein using the polarizable electrode of the electric double layer composed collect the RA current and active material based on nanoporous conductive materials.

26. The method according A.25, characterized in that as the active nanoporous conductive material of the polarizable electrode using nanoporous carbon conductive material or nanoporous material of the electroconductive titanium oxide, or nanoporous material titanium carbide, or mixtures thereof with various combinations.

27. The method according to p, characterized in that the use of nanoporous material, the electrochemical potential of the electrical double layer which is positive relative to the potential of the standard hydrogen reference electrode.

28. The method according to p, characterized in that the use of nanoporous material with the size of the nanopores from 0.2 nm to 5 nm.

29. The method according to p, characterized in that the use of the nanomaterial with a specific surface area of from 600 m2/g to 1800 m2/year

30. The method according to p, characterized in that the use of nanoporous material with a specific pore volume of 0.5 cm3/g to 1.5 cm3/year

31. The method according to p, characterized in that the use of nanoporous material with electrical resistivity of 0.01 Ω·cm to 1000 Ohms·see

32. The method according A.25, characterized in that the use of nanoporous conductive material in the form of powders or granules, or fibers, or plates, or disks.

33. The method according A.25, characterized in that the use of nanoporous materials made of nanoporous carbon powder and a polymeric binder materials.

34. The method according A.25, characterized in that use electrode with the collector current, is made of electrically conductive and resistant to the solutions of materials.

35. The method according to item 21, wherein using the counter-electrode electrochemical cell, made of electrically conductive oxides of transition metals or noble metal oxides or noble metals or their alloys with low values of the overvoltage of oxygen evolution and hydrogen.

36. The method according to item 21, wherein using the electrochemical cell separator made of microporous an ion-conductive material based on polymers that are resistant to inorganic acids.

37. The method according to item 21, wherein the dielectric constant of the solvent multicomponent acidic solutions containing ionic complexes of transition, rare earth and actinoid elements, ranges from 25 to 100.

38. The method according to item 21, wherein filling the nanopores nanoporous conductive material, the initial solution is performed by filling the cells with a solution and curing under normal conditions for 5 to 20 hours

39. The method according to § 38, wherein the electrochemical cell of p is the following casting solution and aging under normal conditions, the solution is subjected to vacuum for maximum filling of the pores.

40. The method according to § 38, characterized in that the ratio of volumes of a solution to a total volume of nanopores active nanoporous material of the polarizable electrode is from 0.8 to 1.2.

41. The method according to item 21, wherein the use solution has a length of Debye shielding, comprising from 0.2 nm to 200 nm.

42. The method according to item 21, wherein the displacement of the nanopores weakly localized in nanopores ion complexes elements hold the pressure of the air or gaseous nitrogen or gaseous carbon dioxide, or water.

43. The method according to item 21, wherein to fill the pores of nanoporous material inorganic acid of high concentration is used, the acid solution with a dielectric constant of not more than 20, in particular solutions of hydrochloric acid, sulfuric acid, phosphoric acid, hydrofluoric acid and mixtures thereof.

44. The method according to item 21, wherein the parameter is selected distribution of pore size nanoporous material and the length value of the Debye screening of multicomponent solution for selective extraction of salt each transition, or rare earth or actinoid elements.

45. The method according to item 21, wherein the removing of the nanopores of the residual ion complexes of transition and/or rare earth, or/and actinoid elements conduct way of the polarization potential of the polarizable electrode with a double electric layer electrochemical cell in the opposite direction of the equilibrium potential.



 

Same patents:

FIELD: metallurgy.

SUBSTANCE: invention can be used in the technology of obtaining the compounds of rare-earth metals at complex processing of apatites, and namely for obtaining of concentrate of rare-earth metals (REM) from phosphogypsum. Method involves sorption of rare-earth metals. At that, prior to sorption, phosphogypsum is crushed in water so that pulp is obtained in the ratio Solid : Liquid=1:(5-10). Sorption is performed by introducing to the obtained pulp of sorbent containing sulphate and phosphate functional groups, at the ratio of Solid : Sorbent=1:(5-10) and mixing during 3-6 h.

EFFECT: increasing REM extraction degree to finished product.

5 tbl, 5 ex

FIELD: metallurgy.

SUBSTANCE: method involves oxidation of micro production wastes at temperature of 550-650°C in air atmosphere for destruction of crystal latitude Nd2Fe14B so that Fe2O3, Nd2O3, Fe2B is formed and moisture and oil is removed. Then, anhydrous fluorides of rare-earth metals are obtained and their metallothermic reduction is performed for production of constant magnets. After oxidation from oxidated microwastes is completed, rare-earth metals are leached with nitric acid with concentration of 1-2 mol/l at temperature of 20-80°C. Obtained nitrate solutions containing rare-earth metals and impurity elements are processed with solution of formic acid with extraction of formiates of rare-earth metals in the form of the deposit cleaned from impurity elements, which includes iron, aluminium, nickel, cobalt, copper and other transition metals.

EFFECT: regeneration of rare-earth metals from production wastes of magnets and obtaining raw material containing rare-earth metals for reutilisation in production of rare-earth constant magnets.

2 cl, 2 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention relates to methods of extracting a concentrate of rare-earth elements from wet-process phosphoric acid, which is obtained in a dihydrate process of processing an apatite concentrate, and can be used in chemical and related industries. The method involves sorption of rare-earth elements and thorium contained in wet-process phosphoric acid at temperature 20-85°C, wherein the sorbent used is a sulphoxide cationite, washing the saturated sorbent with water, desorption of rare-earth elements and thorium with concentrated ammonium sulphate solution to form a desorbate, and treating the desorbate with an ammonia-containing precipitant in form of ammonium carbonate or ammonia gas, which is fed in two steps, wherein at the first step the precipitant is fed until achieving pH 4.5-5.0 with precipitation and separation of a thorium-containing precipitate, and at the second step - until achieving pH of not less than 7 with precipitation and separation of a concentrate of rare-earth elements.

EFFECT: invention increases extraction of rare-earth elements while obtaining a non-radioactive concentrate of rare-earth elements.

4 cl, 4 ex

FIELD: metallurgy.

SUBSTANCE: method to extract holmium (III) cations from nitrate solutions includes ion floatation using an anion-type surfactant as a collector. Besides, the collector is dodecyl sodium sulfate in a concentration corresponding to stoichiometry of the following reaction: Ho+3+3C12H25OSO3Na=Ho[C12H25OSO3]3+3Na+, where Ho+3 - holmium cation, C12H25OSO3Na - sodium dodecyl sulfate. Moreover, ion floatation is carried out at pH=6.6-7.4, which makes it possible to achieve 90% extraction of holmium from aqueous solutions of its salts.

EFFECT: higher extent of holmium extraction.

1 dwg, 1 tbl, 1 ex

FIELD: metallurgy.

SUBSTANCE: invention relates to the method for production of pure lanthanum or its oxides from lean or industrial raw materials by method of ion floatation. The method to extract lanthanum La+3 cations from aqueous solutions of salts includes ion floatation using an anion-type surfactant as a collector. Besides, the collector is dodecyl sodium sulfate in a concentration corresponding to the stoichiometric reaction: La+3+3NaDS=La[DS]3+3Na+, where La+3 - lanthanum cation, NaDS - dodecyl sodium sulfate. Moreover, ion floatation is carried out at pH=7.8-8.1, which makes it possible to achieve 98% extraction of lanthanum from aqueous solutions of its salts.

EFFECT: higher extent of lanthanum extraction.

2 dwg, 1 ex

FIELD: metallurgy.

SUBSTANCE: method for extracting rare-earth elements from the technological and productive solutions containing iron (III) and aluminium, with a pH-0.5÷2.5, includes the sorption of rare-earth elements with strong-acid cation resin. As the strong-acid cation resin the microporous strong-acid cation resin is used based on hypercrosslinked polystyrene having a size of micropores 1-2 nm.

EFFECT: higher efficiency of the process due to greater sorption capacity of the said strong-acid cation resin, high kinetics of sorption and selectivity, improvement of the subsequent quality of eluates and simplification of the process of their further processing.

5 tbl, 5 ex

FIELD: metallurgy.

SUBSTANCE: method of phosphogypsum processing involves leaching of phosphogypsum with sulphuric acid solution with change-over of phosphorus and rare-earth elements to the solution, and gypsum residues is obtained, rare-earth elements are extracted from the solution and the gypsum residue is neutralised with the main calcium compound. In addition, leaching is performed with sulphuric acid solution with concentration of 1-5 wt %. After that, rare-earth elements are extracted from the solution by sorption using sulfocationite in hydrogen or ammonia form with further desorption of rare-earth elements with ammonia sulphate solution. After desorption to the obtained strippant there added is ammonia or ammonium carbonate with deposition and separation of hydroxide or carbon-bearing concentrate of rare-earth elements. Extraction of rare-earth elements of medium and yttrium groups to concentrates is 41-67% and 28-51.4% respectively. Specific consumption of neutralising calcium compound per 1 kg of phosphogypsum has been reduced at least by 1.6 times.

EFFECT: obtaining high-quality hydroxide or carbonate concentrate of rare-earth elements.

4 cl, 4 tbl, 4 ex

FIELD: metallurgy.

SUBSTANCE: method involves leaching rare-earth elements and phosphorus from phosphogypsum. Leaching is carried out using a bacterial complex consisting of several types of acidophilic thionic bacteria in the active growth phase, adapted for active transfer into the liquid phase of phosphorus and rare-earth elements. Leaching is carried out in tank conditions with bacterial population of 107 cells/ml, solid-to-liquid ratio 1:5-1:9, active or moderate aeration and temperature 15-45°C for 3-30 days.

EFFECT: high efficiency of the process of recycling phosphogypsum using a cheap and an ecologically safe method.

2 ex

FIELD: metallurgy.

SUBSTANCE: extraction method of rare-earth elements from solutions containing multiple excess iron (III) and aluminium, with pH=0.5÷2.5 involves sorption using macroporous sulfocationite as sorbent. At that, as sorbent there used is macroporous sulfocationite containing more than 12 to 20% of divinyl benzene.

EFFECT: effective extraction of amount of rare-earth elements from solutions.

4 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: method of extracting cerium cations from aqueous solutions of its salts involves use of a sodium dodecyl sulphate surfactant collector with concentration corresponding to the reaction stoichiometry: Ce+3+3DS-=Ce[DS-]3, where Ce+3 is a cerium cation, DS- is a dodecyl sulphate ion. Cerium cations are extracted via flotoextraction in an organic phase at pH=7.6-8.3. The organic phase used is isooctyl alcohol.

EFFECT: high degree of cerium extraction.

2 dwg

FIELD: metallurgy.

SUBSTANCE: invention relates to mineral stock processing and may be used for extracting gold fractions of grain size smaller than 0.07 mm. Proposed method comprises preparing water suspension with addition of flocculating agent. Damped ground paper bulk is added to said suspension, paper bulk features reduced moisture resistance and mineral component-to-bulk ratio making 1: 0.05. Then, mix is mixed in mixer for 10 s. After mixing, paper bulk is separated on sieve with mesh size not exceeding 0.2 mm. Now, paper bulk is rinsed to produce concentrate to be dried and fused.

EFFECT: higher efficiency, lower costs.

1 ex

FIELD: process engineering.

SUBSTANCE: invention relates to processing natural uranium chemical concentrate. Proposed method comprises concentrate leaching by nitric acid solution to obtain suspension, adding coagulant into suspension and suspension separation. Clarified solution is separated from residue and directed to extraction. Note here that polyacrylamide-based anion coagulant is used and suspension with said coagulant is subjected to permanent magnetic field effects. Coagulant concentration and duration of magnetic field effects are selected to ensure concentration of insoluble residue now exceeding 100 mg/l in clarified solution. In extraction from clarified solution, no antifloating emulsions are observed.

EFFECT: solution suitable for further extraction.

3 cl, 2 tbl

FIELD: chemistry.

SUBSTANCE: method involves transfer of manganese and accompanying impurities into a solution through two-step treatment of the starting material with hydrochloric acid and absorption of chlorine with an alkaline solution. Further, impurities are separated to obtain a manganese salt solution which is then treated. The first step uses waste hydrochloric acid with concentration 1-10% with solid to liquid ratio equal to 1:(3-5). A manganese-containing residue is separated from the obtained pulp, where said residue is then treated at the second step with waste inhibited hydrochloric acid with concentration 20-24% and content of inhibitor of not less than 5 wt %, reaction with iron of which results in insoluble complex compounds, where said inhibitor is in form of quaternary ammonium salts, with molar ratio manganese:HCl=1.0:1.1. The insoluble residue of aluminosilicates is then separated and the manganese salt solution is then processed using existing methods.

EFFECT: obtaining high-quality products.

5 cl, 2 tbl, 2 ex

FIELD: metallurgy.

SUBSTANCE: procedure for extraction of nickel from solutions and purification from impurities: Cr3+, Fe3+, Al3+, Cu2+, Zn2+, Co2+, Fe2+, Mn2+, Ca2+, Mg2+ consists in bringing pH of solutions to values 4.0-6.5, in sorption of nickel at pH=4.0-6.5 from solutions or pulps on sub-acid cationites, in desorption of nickel from saturated cationites with solution of sulphuric or hydrochloric acid with production of solution of nickel strippant. Before desorption saturated cationite is treated with solution of nickel purified from impurities, also with portion of solution of strippant with concentration of nickel higher, than its concentration in source solution or pulp coming to sorption at a value of pH less, than pH of solution or pulp in the process of sorption. Ratio of CNI:ΣCimpurity in solution of strippant changes from 7:1 to 500:1.

EFFECT: more deep purification of solution of nickel strippant from impurities.

4 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to a novel method of removing copper (II) ions from water in the presence of ammonia, which is based on using a floatation reagent in form of β-N-oxyethylhydrazides of aliphatic carboxylic acids of formula (I), where R is a straight-chain radical containing 7-14 carbon atoms.

EFFECT: method ensures high recovery ratio (up to 99,0%) of copper (II) from ammonia media in a single step with relatively low reagent consumption.

2 cl, 2 tbl, 10 ex, 2 dwg

FIELD: process engineering.

SUBSTANCE: invention relates to method of producing iridium from (trifluorophosphine) iridium hydride tetrakis and may be used for production of high-purity metal iridium powder. Proposed method comprises ammonolysis of volatile complex compound of (trifluorophosphine) iridium hydride tetrakis Hlr(PF3)4 with conversion into nonvolatile iridium metallamine by water solution of ammonium. Then, iridium metallamine is dissolved in concentrated hydrogen nitrate and solution is evaporated. Evaporation over, residue is decomposed to sponge-structure metal iridium. Now, the latter is triturated, reduced in hydrogen flow and purified to high-purity iridium.

EFFECT: high-purity iridium powder.

1 ex

FIELD: metallurgy.

SUBSTANCE: procedure for purification of zinc sulphate solution from impurities consists in hydrolytic purification with preliminary iron oxidisation in two stages: first with diluted solution of hydrogen peroxide at temperature 20-55°C and consumption 0.95-1.1 of stoichiometric required amount, then with manganese dioxide contained in electrolytic slime of zinc production.

EFFECT: complete or partial avoiding expenditures for costly oxidant - manganese ore and reduced contents of foreign impurities in zinc sulphate solution.

2 ex

FIELD: metallurgy.

SUBSTANCE: invention relates to metallurgy of noble metals, in particular, to method of processing nitration hydroxides in refinery of platinum metals containing chalcogenides, tin, arsenium and platinum group metals, gold and silver. Proposed method comprises leaching of hydroxides and extracting basic metal compounds from the solution. Hydroxide leaching is carried out for 1-2 h by alkali solution with concentration of 140-180 g/l with l:S ratio varying from 3:1 to 4:1, temperature 80-90°C, and introducing hydrazine hydrate into pulp to reach OVP of minus 400-600 mV relative to reference silver-chloride electrode. Then, alkaline solution is separated from insoluble residue that concentrates platinum metals. Now, extraction of basic metals is carried out in processing alkaline solution by sulfuric acid to pH=4-5 to produce hydroxide precipitate of tin, arsenium, selenium and tellurium, and by filtration, or processing of alkaline solution by sulfuric acid to pH 0.5-1.0 along with adding iron powder to OVP varying from 0 to minus 100 mV, and filtration of obtained cementates obtained on the basis of selenium and tellurium, and processing the solution by alkali to pH = 4-5 with deposition of tin and arsenium hydroxides. Invention allows extracting up to 85% of Se and Te into target products, 90% of Sn and As into secondary hydroxides at minimum transition (less than 1%) into PMH.

EFFECT: over 99% of platinum metals left in refinery cycle, reduced processing cycle.

4 tbl

FIELD: metallurgy.

SUBSTANCE: procedure consists in concentrating refractory ore with successive concentrate fine crumbling to release gold with extracting solution and in mixing fine crumbled concentrate with wastes or by-products of concentrating to facilitate filtering said concentrate mixed with said wastes of concentrating. Here is also disclosed the installation for implementation of the said procedure.

EFFECT: increased rate of processing of refractory mineral ore avoiding harmful effect to environment.

14 cl, 4 dwg, 1 ex

FIELD: chemistry.

SUBSTANCE: electrosorption carbon material is the cathode and is carbon fibric on which there is a layer a conducting polymer - poly-3,4-ethylenedioxythiophene or polyaniline which can chemically reduce ions of noble metals Ag, Au and Pd to metal state. Before passing the aqueous solution to the electrosorption carbon material, a negative potential between -0.5 and -0.3 V is applied relative a silver chloride electrode. Reduction takes place upon contact of the electrosorption carbon material with the aqueous solution in flow mode while feeding the solution at a rate of 10-20 ml per minute per square centimetre of the electrosorption carbon material. Concentration of the extracted metal in the solution is measured and the reduction process is repeated many times.

EFFECT: invention increases efficiency of extracting noble metals, shortens duration of the process of their separation and simplifies and lowers the cost of the extraction process.

4 cl, 3 ex, 1 dwg

FIELD: chemistry.

SUBSTANCE: additive contains the following, wt %: nanostructured boehmite 15-20, surfactants 15-20 and low-viscosity mineral oil - the balance. The break-in oil for internal combustion engine break-in contains mineral oil and said additive in amount of 4-5 wt %.

EFFECT: reducing breaking-in time of friction members.

3 cl, 1 ex

Up!